Mixture comprising sulfonate group-containing compound and method of manufacturing the same, solution composition, polyurethane resin and method of manufacturing the same, and magnetic recording medium

ABSTRACT

An aspect of the present invention relates to a mixture of a sulfonate group-containing compound denoted by general formula (1) with a protonic acid: 
     
       
         
         
             
             
         
       
     
     wherein, in general formula (1), X denotes a divalent linking group; each of R 1  and R 2  independently denotes an alkyl group comprising at least one hydroxyl group and equal to or more than three carbon atoms or an aralkyl group comprising at least one hydroxyl group and equal to or more than eight carbon atoms; and M denotes a cation.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Divisional application of U.S. Ser. No. 12/768,437 filed Apr.27, 2010 which claims the benefit of priority under 35 USC 119 toJapanese Patent Application No. 2009-109683, filed on Apr. 28, 2009, thedisclosures of which are expressly incorporated herein by reference intheir entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a mixture comprising a sulfonategroup-containing compound and to a solution composition prepared fromthe mixture, and more particularly, to a mixture comprising a sulfonategroup-containing compound with good storage stability in organicsolvents and to a solution composition prepared from the mixture.

The present invention further relates to polyurethane resin obtainedusing the above mixture or solution composition as a starting material,to a method of manufacturing the polyurethane resin, and to a magneticrecording medium comprising the above polyurethane resin as binder.

2. Discussion of the Background

In recent years, methods of transmitting information at high speed havedeveloped markedly, making it possible to transmit images and datacomprised of immense amounts of information. As data transmissiontechnology has improved, there has been a demand to further increase therecording density of recording and reproduction devices and recordingmedia for recording, reproducing, and storing information.

The use of microparticulate magnetic powder, the high-degree dispersionof microparticulate magnetic powder, and increasing the smoothness ofthe surface of the magnetic layer are known to be effective ways ofachieving good electromagnetic characteristics in the field ofhigh-density recording. The method of incorporating a sulfonic acid(salt) group, such as SO₃Na group, into the binder is known to enhancethe dispersibility of microparticulate magnetic powder. In thisconnection, reference can be made to Japanese Unexamined PatentPublication (KOKAI) No. 2003-132531 or English language family memberU.S. Pat. No. 6,677,036, which are expressly incorporated herein byreference in their entirety.

The method of employing a sulfonic acid polyol into which a sulfonicacid (salt) group has been incorporated as a starting material diol isan example of a method of incorporating a sulfonic acid (salt) groupinto the polyurethane resins that are widely employed as binders inmagnetic recording media. Polyester sulfonic acid polyols are amongknown sulfonic acid polyols. However, in polyester sulfonic acidpolyols, sulfonic acid (salt) groups become localized in some of theoligomer components, and are present in a nonuniform state. Accordingly,in the polyurethanes obtained using these polyester sulfonic acidpolyols as starting material polyols, the sulfonic acid (salt) groupsare also present in a nonuniform state, in some cases resulting inpolyurethanes containing almost no sulfonic acid (salt) groups. Suchpolyurethanes adsorb poorly to magnetic powder and do not afford gooddispersion-enhancing effects. The polyurethane that does not adsorb maymigrate to the surface of the medium, potentially generating head grimeand compromising running durability.

Accordingly, it is also conceivable to employ a sulfonic acid diolmonomer to obtain a polyurethane resin in which sulfonic acid (salt)groups are uniformly present. An example of such a sulfonic acid diol isN,N-bis(hydroxyalkyl)aminoethyl sulfonate described in JapaneseUnexamined Patent Publication (KOKAI) Heisei No. 3-66660,

However, conventional sulfonic acid diols, including the sulfonic aciddiol described in Japanese Unexamined Patent Publication (KOKAI) HeiseiNo. 3-66660, are highly soluble in water and poorly soluble in organicsolvents. Since polyurethane resins are generally synthesized in organicsolvents, it is difficult to achieve a reaction that proceeds smoothlywith sulfonic acid diols that are poorly soluble in organic solvents.Good solubility in organic solvents is also desirable from theperspective of utility as a starting material in organic synthesis.

In contrast, the present inventors previously discovered a sulfonic acid(salt) group-containing polyol compound with good solubility in organicsolvents, that is described in Japanese Unexamined Patent Publication(KOKAI) No. 2009-96798, published on May 7, 2009, which is expresslyincorporated herein by reference in its entirety. In the presentspecification, the term “sulfonic acid (salt) group” includes thesulfonic acid group (—SO₃H) and sulfonate groups such as —SO₃Na, —SO₃Li,and —SO₃K. The sulfonic acid (salt) group-containing polyol described inJapanese Unexamined Patent Publication (KOKAI) No. 2009-96798 is highlysoluble in organic solvents, and can thus be employed in uniform systemreactions in organic solvents. Accordingly, the above sulfonic acid(salt) group-containing polyol is suitable as an organic synthesisstarting material, including as a starting material of polyurethane.However, research conducted by the present inventors has revealed thatwhen stored in an organic solvent, the above sulfonic acid (salt)group-containing polyol undergoes a substantial change in pH over time.It is required to improve the storage stability in organic solvent toincrease the overall utility as an organic synthesis starting materialof the above sulfonic acid (salt) group-containing polyol compound.

SUMMARY OF THE INVENTION

An aspect of the present invention provides for a sulfonic acid (salt)group-containing polyol compound with good solubility and storagestability in organic solvents.

The present inventors conducted extensive research, resulting in thediscovery that the storage stability in organic solvent of the abovesulfonic acid (salt) group-containing polyol compound could be improvedby placing the base form in the presence of a protonic acid. The presentinvention was devised on that basis.

An aspect of the present invention relates to a mixture of a sulfonategroup-containing compound denoted by general formula (1) with a protonicacid:

wherein, in general formula (1), X denotes a divalent linking group;each of R¹ and R² independently denotes an alkyl group comprising atleast one hydroxyl group and equal to or more than three carbon atoms oran aralkyl group comprising at least one hydroxyl group and equal to ormore than eight carbon atoms; and M denotes a cation.

In general formula (1), each of R¹ and R² may independently denote agroup denoted by general formula (A):

wherein, in general formula (A), * denotes a position of a bond with anitrogen atom, and R^(a) denotes an alkyl group with 2 to 20 carbonatoms, an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7to 20 carbon atoms, an alkoxyalkyl group with 2 to 20 carbon atoms, oran aryloxyalkyl groups with 7 to 20 carbon atoms.

In general formula (1), each of R¹ and R² may independently denote agroup denoted by general formula (B):

wherein, in general formula (B), * denotes a position of a bond with anitrogen atom, R^(b) denotes an alkyl group with 2 to 20 carbon atoms,an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20carbon atoms, an alkoxyalkyl group with 2 to 20 carbon atoms, or anaryloxyalkyl group with 7 to 20 carbon atoms.

The protonic acid may comprise at least one selected from the groupconsisting of a carboxylic acid, sulfonic acid, phosphoric acid,phosphonic acid, and phenol.

The protonic acid may comprise a sulfonic acid group-containing compoundin which M in general formula (1) denotes a hydrogen atom.

The above mixture may comprise 0.05 to 0.50 mole of the protonic acidper 1 mole of the sulfonate group-containing compound.

A further aspect of the present invention relates to a method ofmanufacturing the above mixture by adding a protonic acid to thesulfonate group-containing compound denoted by general formula (1).

The protonic acid may comprise at least one selected from the groupconsisting of a carboxylic acid, sulfonic acid, phosphoric acid,phosphonic acid, and phenol.

The protonic acid may be added in a quantity of 0.05 to 0.50 mole per 1mole of the sulfonate group-containing compound.

A still further aspect of the present invention relates to a method ofmanufacturing the above mixture by, in a step of reacting a sulfonicacid (salt) group-containing amine with an oxilane, conducting thereaction in the presence of 0.50 to 0.95 mole percent of a base relativeto the sulfonic acid (salt) groups contained in the amine.

The sulfonic acid (salt) group-containing amine may be selected from thegroup consisting of an amino benzene sulfonic acid and a salt thereof,and 2-aminoethanesulfonic acid and a salt thereof.

A still further aspect of the present invention relates to a solutioncomposition comprised of an organic solvent in which the above mixtureis dissolved.

The organic solvent may be an aprotic organic solvent.

The aprotic organic solvent may be a solvent selected from the groupconsisting of toluene, 2-butanone, cyclohexanone, and a mixed solventcomprising two or more thereof.

A still further aspect of the present invention relates to apolyurethane resin obtained from starting materials in the form of anisocyanate compound and the above mixture or a solution compositioncomprised of an organic solvent in which the mixture is dissolved.

The polyurethane resin may comprise a sulfonic acid (salt) group in aquantity of 1×10⁻⁵ eq/g to 2×10⁻³ eq/g.

The starting materials may further comprise a diol comprising a(meth)acryloyloxy group.

A still further aspect of the present invention relates to a method ofmanufacturing a polyurethane resin, comprising subjecting the abovemixture or a solution composition comprised of an organic solvent inwhich the mixture is dissolved to an urethane-forming reaction with anisocyanate compound.

The urethane-forming reaction may be conducted in the presence of acatalyst.

The mixture or the solution composition may be subjected to theurethane-forming reaction after adding the catalyst thereto.

A still further aspect of the present invention relates to a magneticrecording medium comprising a magnetic layer comprising a ferromagneticpowder and a binder on a nonmagnetic support, wherein the bindercomprises a polyurethane resin obtained from starting materials in theform of an isocyanate compound and the above mixture or a solutioncomposition comprised of an organic solvent in which the mixture isdissolved.

A still further aspect of the present invention relates to a magneticrecording medium comprising a nonmagnetic layer comprising a nonmagneticpowder and a binder and a magnetic layer comprising a ferromagneticpowder and a binder in this order on a nonmagnetic support, wherein oneor both of the magnetic layer and the nonmagnetic layer comprise thebinder in the form of a polyurethane resin, the polyurethane resin beingobtained from starting materials in the form of an isocyanate compoundand the above mixture or a solution composition comprised of an organicsolvent in which the mixture is dissolved.

The present invention permits the long-term storage of a sulfonategroup-containing compound with good solubility in organic solvents in astable state in organic solvents. This can enhance the utility of thesulfonate group-containing compound as a starting material in organicsynthesis.

Other exemplary embodiments and advantages of the present invention maybe ascertained by reviewing the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Unless otherwise stated, a reference to a compound or component includesthe compound or component by itself, as well as in combination withother compounds or components, such as mixtures of compounds.

As used herein, the singular forms “a,” “an,” and “the” include theplural reference unless the context clearly dictates otherwise.

Except where otherwise indicated, all numbers expressing quantities ofingredients, reaction conditions, and so forth used in the specificationand claims are to be understood as being modified in all instances bythe term “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention. Atthe very least, and not to be considered as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should be construed in light of the number ofsignificant digits and ordinary rounding conventions.

Additionally, the recitation of numerical ranges within thisspecification is considered to be a disclosure of all numerical valuesand ranges within that range. For example, if a range is from about 1 toabout 50, it is deemed to include, for example, 1, 7, 34, 46.1, 23.7, orany other value or range within the range.

The following preferred specific embodiments are, therefore, to beconstrued as merely illustrative, and non-limiting to the remainder ofthe disclosure in any way whatsoever. In this regard, no attempt is madeto show structural details of the present invention in more detail thanis necessary for fundamental understanding of the present invention; thedescription taken with the drawings making apparent to those skilled inthe art how several forms of the present invention may be embodied inpractice.

Mixture

The present invention relates to a mixture of a sulfonategroup-containing compound denoted by general formula (1) with a protonicacid.

In general formula (1), X denotes a divalent linking group; each of R¹and R² independently denotes an alkyl group comprising at least onehydroxyl group and equal to or more than three carbon atoms or anaralkyl group comprising at least one hydroxyl group and equal to ormore than eight carbon atoms; and M denotes a cation.

In contrast to the poor solubility in organic solvents of conventionallyknown sulfonic acid diols, the sulfonate group-containing compounddenoted by general formula (1) can exhibit good solubility in organicsolvents. Since organic synthesis reactions are generally conducted inorganic solvents, compounds that dissolve readily in organic solventsare suitable as organic synthesis starting materials. In the mixture ofthe present invention, by placing such a sulfonate group-containingcompound in the presence of a protonic acid, the change over time in thepH of the sulfonate group-containing compound in organic solvent can besuppressed and thus good storage stability can be achieved. This goodstorage stability in organic solvents is extremely advantageous forstoring and handling the compound in the form of a solution composition.

Details of the mixture of the present invention will be described below.

Sulfonate Group-Containing Compound Denoted by General Formula (1)

In general formula (1), X denotes a divalent linking group, desirablyhaving 2 to 20 carbon atoms from the perspective of solubility inorganic solvents. A divalent hydrocarbon group is desirable; an alkylenegroup, arylene group, or a combination of two or more of these groups ispreferred; an alkylene group or an arylene group is of greaterpreference; an ethylene group or a phenylene group is of still greaterpreference; and an ethylene group is optimal.

Examples of the phenylene group are o-phenylene, m-phenylene, andp-phenylene groups. An o-phenylene or m-phenylene group is desirable,and an m-phenylene group is preferred.

The above alkylene group desirably comprises equal to or more than 2 butequal to or less than 20, preferably equal to or more than 2 but equalto or less than 4, and more preferably 2, carbon atoms. The alkylenegroup may be a linear alkylene group or branched alkylene group; alinear alkylene group is desirable.

The above arylene group desirably comprises equal to or more than 6 butequal to or less than 20, preferably equal to or more than 6 but equalto or less than 10, and more preferably 6, carbon atoms.

The above alkylene and arylene groups may be substituted orunsubstituted. Examples of substituents are given below. The alkylenegroup or arylene group is desirable comprised of just carbon atoms andhydrogen atoms. In the present invention, when a substituent is presenton a given group, the term “number of carbon atoms” of that group refersto the number of carbon atoms excluding the substituent.

Examples of substituents that are optionally present on the alkylenegroup are: aryl groups, halogen atoms (fluorine, chlorine, bromine, andiodine atoms), alkoxy groups, aryloxy groups, and alkyl groups.

Examples of substituents that are optionally present on the arylenegroup are: alkyl groups, halogen atoms (fluorine, chlorine, bromine, andiodine atoms), alkoxy groups, aryloxy groups, and aryl groups.

In general formula (1), each of R¹ and R² independently denotes an alkylgroup comprising at least one hydroxyl group and equal to or more thanthree carbon atoms or an aralkyl group comprising at least one hydroxylgroup and equal to or more than eight carbon atoms. The alkyl group andaralkyl group may have substituents other than hydroxyl groups.

In addition to hydroxyl groups, the above alkyl group and aralkyl groupmay comprise substituents in the form of alkoxy groups, aryloxy groups,halogen atoms (fluorine, chlorine, bromine, and iodine atoms), sulfonylgroups, and silyl groups, for example. Of these, alkoxy groups andaryloxy groups are desirable; alkoxy groups having 1 to 20 carbon atomsand aryloxy groups having 6 to 20 carbon atoms are preferred; andphenoxy groups and alkoxy groups having 1 to 4 carbon atoms are ofgreater preference.

These alkyl groups and aralkyl groups may be linear or branched.

One or more hydroxyl groups are contained, 1 or 2 are desirable, and 1is preferred, in each of R¹ and R². From the perspective of utility as apolyurethane starting material, the sulfonate group-containing compounddenoted by general formula (1) is preferably a sulfonategroup-containing diol compound.

From the perspective of solubility in organic solvents, the alkyl groupin R¹ and R² comprises equal to or more than 3, desirably 3 to 22,preferably 4 to 22, and more preferably, 4 to 8 carbon atoms.

From the perspective of solubility in organic solvents, the aralkylgroup in R¹ and R² comprises equal to or more than 8, desirably 8 to 22,preferably 8 to 12, and more preferably, 8 carbon atoms. In the aralkylgroup contained in R¹ and R², saturated hydrocarbon chains are desirablypresent at the α-position and β-position of the nitrogen atom. In thatcase, a hydroxyl group may be present at the β-position of a nitrogenatom.

In R¹ and R², a hydroxyl group is desirably not present at theα-position of a nitrogen atom, one hydroxyl group is desirably presentat the least the β-position of a nitrogen atom, and a single hydroxylgroup is preferably present at the β-position of a nitrogen atom. Thepresence of a hydroxyl group at the β-position of a nitrogen atom canfacilitate synthesis and enhance solubility in organic solvents.

Each of R¹ and R² independently preferably denotes an alkyl groupcomprising at least one hydroxyl group and 3 to 22 carbon atoms, anaralkyl group comprising at least one hydroxyl group and 8 to 22 carbonatoms, an alkoxyalkyl group comprising at least one hydroxyl group and 4to 22 carbon atoms, or an aryloxyalkyl group comprising at least onehydroxyl group and 9 to 22 carbon atoms. An alkyl group comprising atleast one hydroxyl group and 4 to 22 carbon atoms, an aralkyl groupcomprising at least one hydroxyl group and 8 to 22 carbon atoms, analkoxyalkyl group comprising at least one hydroxyl group and 4 to 22carbon atoms, or an aryloxyalkyl group comprising at least one hydroxylgroup and 9 to 22 carbon atoms is preferred.

Specific examples of alkyl groups comprising at least one hydroxyl groupand equal to or more than 3 carbon atoms are: 2-hydroxypropyl groups,2-hydroxybutyl groups, 2-hydroxypentyl groups, 2-hydroxyhexyl groups,2-hydroxyoctyl groups, 2-hydroxy-3-methoxypropyl groups,2-hydroxy-3-ethoxypropyl groups, 2-hydroxy-3-butoxypropyl groups,2-hydroxy-3-phenoxypropyl groups, 2-hydroxy-3-methoxybutyl groups,2-hydroxy-3-methoxy-3-methylbutyl groups, 2,3-dihydroxypropyl groups,3-hydroxypropyl groups, 3-hydroxybutyl groups, 4-hydroxybutyl groups,1-methyl-2-hydroxyethyl groups, 1-ethyl-2-hydroxyethyl groups,1-propyl-2-hydroxyethyl groups, 1-butyl-2-hydroxyethyl groups,1-hexyl-2-hydroxyethyl groups, 1-methoxymethyl-2-hydroxyethyl groups,1-ethoxymethyl-2-hydroxyethyl groups, 1-butoxymethyl-2-hydroxyethylgroups, 1-phenoxymethyl-2-hydroxyethyl groups,1-(1-methoxyethyl)-2-hydroxyethyl groups,1-(1-methoxy-1-methylethyl)-2-hydroxyethyl groups, and1,3-dihydroxy-2-propyl groups. Of these, 2-hydroxybutyl groups,2-hydroxy-3-methoxypropyl groups, 2-hydroxy-3-butoxypropyl groups,2-hydroxy-3-phenoxypropyl groups, 1-methyl-2-hydroxyethyl groups,1-methoxymethyl-2-hydroxyethyl groups, 1-butoxymethyl-2-hydroxyethylgroups, and 1-phenoxyethyl-2-hydroxyethyl groups are desirable examples.

Specific examples of aralkyl groups comprising at least one hydroxylgroup and equal to or more than 8 carbon atoms are:2-hydroxy-2-phenylethyl groups, 2-hydroxy-2-phenylpropyl groups,2-hydroxy-3-phenylpropyl groups, 2-hydroxy-2-phenylbutyl groups,2-hydroxy-4-phenylbutyl groups, 2-hydroxy-5-phenylpentyl groups,2-hydroxy-2-(4-methoxyphenyl)ethyl groups,2-hydroxy-2-(4-phenoxyphenyl)ethyl groups,2-hydroxy-2-(3-methoxyphenyl)ethyl groups,2-hydroxy-2-(4-chlorophenyl)ethyl groups,2-hydroxy-2-(4-hydroxyphenyl)ethyl groups, 2-hydroxy-3-(4-methoxyphenyl)propyl groups, 2-hydroxy-3-(4-chlorophenyl)propyl groups,1-phenyl-2-hydroxyethyl groups, 1-methyl-1-phenyl-2-hydroxyethyl groups,1-benzyl-2-hydroxyethyl groups, 1-ethyl-1-phenyl-2-hydroxyethyl groups,1-phenethyl-2-hydroxyethyl groups, 1-phenylpropyl-2-hydroxyethyl groups,1-(4-methoxyphenyl)-2-hydroxyethyl groups,1-(4-phenoxyphenyl)-2-hydroxyethyl groups,1-(3-methoxyphenyl)-2-hydroxyethyl groups,1-(4-chlorophenyl)-2-hydroxyethyl groups,1-(4-hydroxyphenyl)-2-hydroxyethyl groups, and1-(4-methoxyphenyl)-3-hydroxy-2-propyl groups. Of these,2-hydroxy-2-phenylethyl groups and 1-phenyl-2-hydroxyphenyl groups aredesirable examples.

The compound denoted by general formula (1) desirably comprises one ormore aromatic ring within the molecule to enhance solubility in organicsolvents.

In general formula (1), R¹ and R² may be identical or different, but aredesirably identical to facilitate synthesis.

In formula (1), each of R¹ and R² desirably denotes a group with equalto or more than five carbon atoms. In general formula (1), each of R¹and R² is desirably a group comprising an aromatic ring and/or an etherbond.

An example of a desirable embodiment of the compound denoted by generalformula (1) is a compound in which each of R¹ and R² independentlydenotes the group denoted by general formula (A) below or the groupdenoted by general formula (B) below.

In general formula (A), * denotes a position of a bond with a nitrogenatom, and R^(a) denotes an alkyl group with 2 to 20 carbon atoms, anaryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20carbon atoms, an alkoxyalkyl group with 2 to 20 carbon atoms, or anaryloxyalkyl groups with 7 to 20 carbon atoms.

In general formula (B), * denotes a position of a bond with a nitrogenatom, R^(b) denotes an alkyl group with 2 to 20 carbon atoms, an arylgroup with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbonatoms, an alkoxyalkyl group with 2 to 20 carbon atoms, or anaryloxyalkyl group with 7 to 20 carbon atoms.

That is, general formula (2) denotes a compound having the group denotedby general formula (A) above and general formula (3) denotes a compoundhaving the group denoted by general formula (B) above.

In general formula (2), each of R²¹ and R²² is independently defined asbeing identical to R^(a) in general formula (A), and X and M areidentically defined with X and M, respectively, in general formula (1).

In general formula (3), each of R³¹ and R³² is independently defined asbeing identical to R^(b) in general formula (B), and X and M areidentically defined with X and M, respectively, in general formula (1).

Each of R^(a) and R^(b) above (R^(a) and R^(b) will be collectivelyreferred to as “R” hereinafter) independently denotes an alkyl groupwith 2 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, anaralkyl group with 7 to 20 carbon atoms, an alkoxyalkyl group with 2 to20 carbon atoms, or an aryloxyalkyl group with 7 to 20 carbon atoms.

The alkyl group denoted by R has 2 to 20, desirably 2 to 8, andpreferably, 2 to 4 carbon atoms.

The aryl group denoted by R has 6 to 20, desirably 6 to 10, andpreferably, 6 carbon atoms.

The aralkyl group denoted by R has 7 to 20, desirably 7 to 11 carbonatoms.

The alkoxyalkyl group denoted by R has 2 to 20, desirably 2 to 12, andpreferably, 2 to 5 carbon atoms.

The aryloxyalkyl group denoted by R has 7 to 20, desirably 7 to 12, andpreferably, 7 carbon atoms.

Each of the alkyl groups, aryl groups, aralkyl groups, alkoxyalkylgroups, and aryloxyalkyl groups denoted by R may be substituted orunsubstituted. Examples of substituents that may be present on the groupdenoted by R are halogen atoms (fluorine, chlorine, bromine, and iodineatoms), hydroxy groups, sulfonyl groups, and silyl groups.

The above alkyl group and aralkyl group may be linear or branched.

Each of the groups denoted by R desirably has two or more carbon atoms.Each of the groups denoted by R desirably comprises an aromatic ringand/or an ether bond.

The groups denoted by R are desirably ethyl groups, methoxymethylgroups, butoxymethyl groups, phenoxymethyl groups, or phenyl groups, andpreferably methoxymethyl groups, butoxymethyl groups, phenoxymethylgroups, or phenyl groups.

In general formula (2), R²¹ and R²² may be identical or different, butare desirably identical to facilitate synthesis. The same applies to R³¹and R³² in general formula (3).

In general formula (1), M denotes a cation. This cation may be aninorganic cation or an organic cation. The cation electricallyneutralizes the —SO₃ ⁻ in general formula (1). It is not limited to amonovalent cation, and can be a divalent or greater cation. A monovalentcation is desirable. When the valence of the cation denoted by M isgiven by n, M denotes (1/n) moles of the cation relative to the compounddenoted by general formula (1).

The inorganic cation is not specifically limited; desirable examples arealkali metal ions and alkaline earth metal ions. Alkali metal ions arepreferred examples, and Li⁺, Na⁺, and K⁺ are examples of greaterpreference.

Examples of organic cations are ammonium ions, quaternary ammonium ions,and pyridinium ions.

Example compounds (S-1) to (S-51) below are desirable specific examplesof the compound denoted by general formula (1). However, the presentinvention is not limited to these compounds. In the specific examplesbelow, “Ph” denotes a phenyl group.

In the mixture of the present invention, the protonic acid that isincorporated along with the sulfonate group-containing compound can beany acid capable of releasing a proton, whether organic or inorganic.Specific examples are: carboxylic acids, sulfonic acids, phosphoricacids, phosphonic acids, and phenols. Examples of organic carboxylicacids are acetic acid, propionic acid, and octanoic acid. Acetic acidand octanoic acid are desirable. Examples of organic sulfonic acids arebenzenesulfonic acid and p-toluenesulfonic acid.

The mixture of the present invention can contain, as a protonic acid, asulfonic acid group-containing compound in which M in general formula(1) denotes a hydrogen atom. For example, a mixture comprising asulfonate group-containing compound in which M denotes a cation ingeneral formula (1) and a sulfonic acid group-containing compounddiffering from this compound only in that M denotes a hydrogen atom ingeneral formula (1) can be obtained by Manufacturing Method 2, describedfurther below. Further, a protonic acid in the form of a sulfonic acidgroup-containing compound in which M denotes a hydrogen atom in generalformula (1) can be added to the sulfonate group-containing compounddenoted by general formula (1) by Manufacturing Method 1, describedfurther below. The sulfonic acid group-containing compound that is addedcan be obtained, for example, by subjecting the sulfonategroup-containing compound denoted by general formula (1) to an ionexchange.

From the perspective of effectively suppressing the change in pH overtime of the compound denoted by general formula (1) in organic solvents,the mixture of the present invention desirably contains 0.05 to 0.50mole of protonic acid, preferably 0.05 to 0.30 mole of protonic acid,per 1 mole of the compound denoted by general formula (1).

The mixture of the present invention may be a solid or a liquidsubstance. It desirably contains an organic solvent in addition to thecompound denoted by general formula (1) and a protonic acid. The mixtureof the present invention may be contained in a dissolved sate or in asuspended state in the organic solvent. For use in an organic synthesisreaction in a uniform system, it is desirably contained in a dissolvedstate in the organic solvent. That is, the compound of the presentinvention is desirably contained in a solution composition comprised ofan organic solvent in which the mixture of the present invention isdissolved.

The solution composition will be described in greater detail below.

Solution Composition

The present invention relates to a solution composition comprised of anorganic solvent in which the mixture of the present invention isdissolved. The solution composition of the present invention is usefulas an organic synthesis starting material because it has good storagestability and does not undergo a major change in pH over time. Themixture of the present invention need only be dissolved in the solutioncomposition of the present invention to a degree of visibletransparency.

Examples of the organic solvent are: alcohol solvents such as methanol,ethanol, propanol, isopropanol, and butanol; nitrile-based solvents suchas acetonitrile; ketone-based solvents such as acetone, methyl ethylketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, andisophorone; ester-based solvents such as methyl acetate, ethyl acetate,and ethyl lactate; ether-based solvents such as dioxane andtetrahydrofuran; aromatic solvents such as toluene and xylene; sulfoxidesolvents such as dimethyl sulfoxide; methylene chloride; chloroform; andcyclohexane.

Of these, from the perspective of utility in organic synthesis reactionssuch as polyurethane synthesis, aprotic solvents are desirable; ketoneand aromatic solvents are preferred; toluene, 2-butanone, cyclohexanone,and mixed solvents comprising two or more thereof are of greaterpreference; and cyclohexanone is of even greater preference.

The solution composition of the present invention can be prepared byadding the mixture of the present invention to an organic solvent andstirring and the like as needed. The content of the mixture of thepresent invention in the solution composition of the present inventionis desirably set to yield a content of equal to or greater than 10weight parts, preferably equal to or greater than 20 weight parts, morepreferably equal to or greater than 40 weight parts, and still morepreferably, 40 to 90 weight parts of the compound denoted by generalformula (1) per 100 weight parts of organic solvent.

Method of Manufacturing Mixture

The present invention further relates to a method of manufacturing themixture of the present invention (referred to as “Manufacturing Method1” hereinafter) by adding a protonic acid to the sulfonategroup-containing compound denoted by general formula (1), and a methodof manufacturing the mixture of the present invention (referred to as“Manufacturing Method 2” hereinafter) in a step of reacting a sulfonicacid (salt) group-containing amine with an oxilane in which the reactionis conducted in the presence of 0.50 to 0.95 mole percent of a baserelative to the sulfonic acid (salt) groups contained in the amine.Manufacturing Methods 1 and 2 will be sequentially described below.

Manufacturing Method 1

In Manufacturing method 1, the mixture of the present invention ismanufactured by adding a protonic acid to the sulfonate group-containingcompound denoted by general formula (1). The details of the sulfonategroup-containing compound denoted by general formula (1) are as setforth above.

The sulfonate group-containing compound denoted by general formula (1)can be synthesized by reacting a sulfonic acid (salt) group-containingamine with an oxilane in the presence of a base. The reaction isdesirably conducted in a solvent that contains water and preferablyconducted in water. The reaction conditions, the types of startingmaterials, the solvent employed, and the like can be suitably set.

Examples of the sulfonic acid (salt) group-containing amine areaminoalkane sulfonates and salts thereof and aminoarene sulfonates andsalts thereof. Amino benzene sulfonic acid and salts thereof and2-aminoethanesulfonic acid and salts thereof are desirable.

Examples of the oxilane are alkylene oxide and glycidyl ether. It can beselected based on the structure of the sulfonate group-containingcompound being targeted. Specific examples of alkylene oxides are:ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide,styrene oxide, and cyclohexanone oxide. Specific examples of glycidylethers are: methyl glycidyl ether, ethyl glycidyl ether, butyl glycidylether, phenyl glycidyl ether, and 2-ethylhexyl glycidyl ether.

A single base may be independently employed, or two or more bases may beemployed in combination as the above base. The base that is employed isnot specifically limited other than that it be able to provide a cationcapable of becoming M in general formula (1). An alkali metal hydroxideis desirable. Specific examples are potassium hydroxide, sodiumhydroxide, and lithium hydroxide.

The method used to isolate the compound denoted by general formula (1)may depend on the above-described base that are employed and the like.However, by way of example, a high purity sulfonate group-containingcompound can be obtained by adding toluene dropwise to the reactionsolution, precipitating the sulfonate group-containing compound,fractionating the mixture by filtration, decantation, or the like, anddrying the product. The sulfonate group-containing compound obtained canbe converted to other sulfonate group-containing compounds through saltexchange by known methods.

The type and quantity of protonic acid that is added to the compounddenoted by general formula (1) (the blending ratio relative to thecompound denoted by general formula (1)) are as set forth above. Thecompound denoted by general formula (1) and the protonic acid aredesirably mixed in an organic solvent. The details of the organicsolvent employed here are as set forth for the solution composition ofthe present invention above.

Manufacturing Method 2

Manufacturing method 2 is a method of manufacturing the mixture of thepresent invention in a step of reacting a sulfonic acid (salt)group-containing amine with an oxilane in which the reaction isconducted in the presence of 0.50 to 0.95 mole percent of a baserelative to the sulfonic acid (salt) groups contained in the amine. Thedetails of the sulfonic acid (salt) group-containing amine, oxilane, andbase in Manufacturing method 2 are as set forth above for Manufacturingmethod 1. When the quantity of base employed is equal to or more than1.0 equivalent of the sulfonic acid (salt) group-containing amine, it ispossible to obtain a product in the form of a sulfonate group-containingcompound in which M in general formula (1) is a cation (also referred toas the “base form” hereinafter). At from greater than 0 equivalent butless than 1.0 equivalent, a compound in which M in general formula (1)is a hydrogen atom (protonic acid; also referred to as the “acid form”hereinafter) is obtained in addition to the base form, yielding amixture of the acid form and the base form. The mixture of the presentinvention can be obtained. However, when the quantity of base relativeto the sulfonic acid (salt) groups contained in the sulfonic acid (salt)group-containing amine is less than 0.50 mole percent, the reaction doesnot proceed smoothly. When this quantity exceeds 0.95 mole percent, thesolvent stability of the mixture obtained decreases. Accordingly, inManufacturing method 2, a sulfonic acid (salt) group-containing amineand oxilane are reacted in the presence of 0.50 to 0.95 mole percent ofa base relative to the sulfonic acid (salt) groups contained in thesulfonic acid (salt) group-containing amine. Thus, the mixture of thepresent invention can be obtained as a mixture of the acid form and baseform with good solution stability. The quantity of base relative to thesulfonic acid (salt) groups contained in the sulfonic acid (salt)group-containing amine is desirably 0.70 to 0.95 mole percent. As setforth above, the reaction is desirably conducted in a solvent thatcontains water, preferably in water.

Polyurethane Resin

The polyurethane resin of the present invention is a polyurethane resinthat is obtained from starting materials in the form of an isocyanatecompound and the mixture of the present invention or the solutioncomposition of the present invention.

The method of employing a sulfonic acid polyol into which has beenincorporated a sulfonic acid (salt) group as a starting material diol isan example of a method of incorporating a sulfonic acid (salt) groupinto the polyurethane resins that are widely employed as binder inmagnetic recording media. Polyester sulfonic acid polyols are amongknown sulfonic acid polyols. However, the sulfonic acid (salt) groups inpolyester sulfonic acid polyols become localized on certain oligomercomponents, and are present in a nonuniform state. Accordingly, inpolyurethanes obtained using such polyester sulfonic acid polyols asstarting material diols, the sulfonic acid (salt) groups are alsopresent in a nonuniform state. In some cases, this results in theproduction of a polyurethane that contains almost no sulfonic acid(salt) groups. Such polyurethanes adsorb poorly to magnetic powder andcannot produce a good dispersion-enhancing effect. The polyurethane thatis unable to adsorb may migrate to the medium surface, potentiallygenerating head grime and compromising running durability. By contrast,the polyurethane resin of the present invention comprises the sulfonategroup-containing compound denoted by general formula (1) as a startingmaterial. The sulfonate group-containing compound denoted by generalformula (1) is highly soluble in the organic solvents employed inpolyurethane polymerization. Further, since it is a monomer sulfonategroup-containing polyol, the sulfonate groups (sulfonate groups andsulfonic acid groups when employing a mixture of the base form and theacid form) can be uniformly incorporated into the polyurethane. Apolyurethane resin in which adsorptive functional groups in the form ofsulfonic acid (salt) groups have been uniformly incorporated in thisfashion permits a high degree of dispersion of powders such as magneticpowder and nonmagnetic powder in coating materials. Coatings formed bycoating such coating materials are highly smooth. As a result, itbecomes possible to obtain a magnetic recording medium with goodelectromagnetic characteristics.

The details of the mixture and solution composition of the presentinvention are as set forth above.

A bifunctional or greater multifunctional isocyanate compound (alsoreferred to hereinafter as a “polyisocyanate”) can be employed as theisocyanate compound. Examples of polyisocyanates that can be employed asstarting materials are: diphenylmethane diisocyanate (MDI), 2,4-trilenediisocyanate (TDI), 2,6-TDI, 1,5-napththalene diisocyanate (NDI),tolidine diisocyanate (TODI), p-phenylene diisocyanate, xylylenediisocyanate (XDI), and other aromatic diisocyanates;transcyclohexane-1,4-diisocyanate, hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate(H₆XDI), hydrogenated diphenylmethane diisocyanate (H₁₂MDI), and otheraliphatic and alicyclic diisocyanates.

In addition to the mixture or solution composition of the presentinvention and the isocyanate compound, a polyol can be included amongthe above starting materials. Polyols that can be employed are thevarious polyols that are generally employed as starting materials ofpolyurethane. For example, known polyester polyols, polyether polyols,polyether-ester polyols, polycarbonate polyols, polyolefin polyols, anddimer diols may be employed as necessary. Of these, the polyesterpolyols and polyether polyols are desirable.

The polyester polyol is obtained by polycondensing a polycarboxylic acid(polybasic acid) with a polyol, and desirably obtained by reacting adibasic acid (dicarboxylic acid) with a diol. Dibasic acid componentsthat can be employed in the polyester polyol are not specificallylimited. Adipic acid, azelaic acid, phthalic acid, sodiumsulfoisophthalic acid, and the like are desirable. Desirable diolsinclude those having branched side chains, such as2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, and3-methyl-1,5-pentanediol.

Polyether polyols with cyclic structures, such as polypropylene oxideadducts of bisphenol A and polyethylene oxide adducts of bisphenol A,are desirable.

In addition to the above polyol, as needed, a known short-chain diolwith a molecular weight of about 200 to 500 can be employed as achain-extending agent. Of these, aliphatic diols having a branched sidechain with two or more carbon atoms, ether compounds having cyclicstructures, short-chain diols having bridged hydrocarbon structures, andshort-chain diols having spiro structures are desirable.

Further, a diol comprising at least one acrylic double bond within themolecule can be employed to impart a radiation curing property. The term“acrylic double bond” referred to in this context means a residue(acryloyl group or methacryloyl group) of acrylic acid, acrylic acidester, acrylamide, methacrylic acid, methacrylic acid ester, or amidemethacrylate. Of these, a diol having at least one (meth)acryloyloxygroup is desirable, and a diol having at least one acryloyloxy group ispreferred.

The following are examples of aliphatic diols having a branched sidechain with two or more carbons: 2-methyl-2-ethyl-1,3-propanediol,3-methyl-3-ethyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol,3-methyl-3-propyl-1,5-pentanediol, 2-methyl-2-butyl-1,3-propanediol,3-methyl-3-butyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol,3,3-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol,3-ethyl-3-butyl-1,5-pentanediol, 2-ethyl-2-propyl-1,3-propanediol,3-ethyl-3-propyl-1,5-pentanediol, 2,2-dibutyl-1,3-propanediol,3,3-dibutyl-1,5-pentanediol, 2,2-dipropyl-1,3-propanediol,3,3-dipropyl-1,5-pentanediol, 2-butyl-2-propyl-1,3-propanediol,3-butyl-3-propyl-1,5-pentanediol, 2-ethyl-1,3-propanediol,2-propyl-1,3-propanediol, 2-butyl-1,3-propanediol,3-ethyl-1,5-pentanediol, 3-propyl-1,5-pentanediol,3-butyl-1,5-pentanediol, 3-octyl-1,5-pentanediol,3-myristyl-1,5-pentanediol, 3-stearyl-1,5-pentanediol,2-ethyl-1,6-hexanediol, 2-propyl-1,6-hexanediol, 2-butyl-1,6-hexanediol,5-ethyl-1,9-nonanediol, 5-propyl-1,9-nonanediol, and5-butyl-1,9-nonanediol.

Of these, 2-ethyl-2-butyl-1,3-propanediol and2,2-diethyl-1,3-propanediol are desirable.

Examples of ether compounds having cyclic structures are ethylene oxideadducts of bisphenol A, propylene oxide adducts of bisphenol A, ethyleneoxide adducts of hydrogenated bisphenol A, and propylene oxide adductsof hydrogenated bisphenol A.

At least one structure selected from the group consisting of formulas(1) to (3) below is desirable as a bridged hydrocarbon structure orspiro structure.

Specific examples of short-chain diols having a bridged hydrocarbonstructure are: bicyclo[1.1.0]butanediol, bicyclo[1.1.1]pentanediol,bicyclo[2.1.0]pentanediol, bicyclo[2.1.1]hexanediol,bicyclo[3.1.0]hexanediol, bicyclo[2.2.1]heptanediol,bicyclo[3.2.0]heptanediol, bicyclo[3.1.1]heptanediol,bicyclo[2.2.2]octanediol, bicyclo[3.2.1]octanediol,bicyclo[4.2.0]octanediol, bicyclo[5.2.0]nonanediol,bicyclo[3.3.1]nonanediol, bicyclo[3.3.2]decanediol,bicyclo[4.2.2]decanediol, bicyclo[4.3.3]dodecanediol,bicyclo[3.3.3]undecanediol, bicyclo[1.1.0]butanedimethanol,bicyclo[1.1.1]pentanedimethanol, bicyclo[2.1.0]pentanedimethanol,bicyclo[2.1.1]hexanedimethanol, bicyclo[3.1.0]hexanedimethanol,bicyclo[2.2.1]heptanedimethanol, bicyclo[3.2.0]heptanedimethanol,bicyclo[3.1.1]heptanedimethanol, bicyclo[2.2.2]octanedimethanol,bicyclo[3.2.1]octanedimethanol, bicyclo[4.2.0]octanedimethanol,bicyclo[5.2.0]nonanedimethanol, bicyclo[3.3.1]nonanedimethanol.bicyclo[3.3.2]decanedimethanol, bicyclo[4.2.2]decanedimethanol,bicyclo[4.3.3]dodecanedimethanol, bicyclo[3.3.3]undecanedimethanol,tricyclo[2.2.1.0]heptanediol, tricyclo[5.2.1.0^(2,6)]decanediol,tricyclo[4.2.1.2^(7,9)]undecanediol,tricyclo[5.4.0.0^(2,9)]undecanediol, tricyclo[5.3.1.1]dodecanediol,tricyclo[4.4.1.1]dodecanediol, tricyclo[7.3.2.0^(5,13)]tetradecanediol,tricyclo[5.5.1.0^(3,11)]tridecanediol,tricyclo[2.2.1.0]heptanedimethanol,tricyclo[5.2.1.0^(2,6)]decanedimethanol,tricyclo[4.2.1.2^(7,9)]undecanedimethanol,tricyclo[5.4.0.0^(2,9)]undecanedimethanol,tricyclo[5.3.1.1]dodecanedimethanol,tricyclo[4.4.1.1]dodecanedimethanol,tricyclo[7.3.2.0^(5,13)]tetradecanedimethanol, andtricyclo[5.5.1.0^(3,11)]-tridecanedimethanol.

Of these, tricyclo[5.2.1.0^(2,6)]decanedimethanol is a desirableexample.

Specific examples of short-chain diols having spiro structures are:spiro[3.4]octanedimethanol, Spiro[3.4]heptanedimethanol,Spiro[3.4]decanedimethanol, dispiro[5.1.7.2]heptadecanedimethanol,cyclopentanespirocyclobutanedimethanol,cyclohexanespirocyclopentanedimethanol, spirobicyclohexanedimethanol,andbis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-hetraoxaspiro[5.5]undecane.

Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane isdesirable.

Specific examples of diols comprising at least one acrylic double bondwithin the molecule are glycerol monoacrylate and glycerolmonomethacrylate (Blemmer GLM, made by NOF Corporation) and bisphenol Atype epoxy acrylate (Epoxyester 3000A, made by Kyoeisha Chemical Co.,Ltd.).

The above polyurethane resin can be manufactured by polymerizing(polyadding) the mixture or solution composition of the presentinvention, an additional polyol, an isocyanate, and a chain-extendingagent, as needed, in the presence of a catalyst. The compound denoted bygeneral formula (1) is desirably added in a quantity yielding asulfonate group content of equal to or greater than 1×10⁻⁵ eq/g butequal to or less than 2×10⁻³ eq/g in the polyurethane resin. Theadditional polyol is desirably added within a range of 20 to 45 weightpercent. The isocyanate is desirably added in a quantity yielding aurethane group concentration falling within a range of 2.5 to 4.5 mmol/gin the polyurethane resin.

Known urethane resin polymerization catalysts may be employed ascatalysts. Examples are tertiary amine catalysts and organic tincatalysts. Examples of tertiary amine catalysts are diethylene triamine,N-methylmorpholine, and tetramethyl hexamethylene diamine. Examples oforganic tin catalysts are dibutyltin dilaurate and tin octoate. Anorganic tin catalyst is desirably employed as the catalyst.

The quantity of catalyst added is desirably 0.01 to 5 weight parts,preferably 0.01 to 1 weight part, and more preferably, 0.01 to 0.1weight part, per the combined weight of the compound denoted by generalformula (1), the other polyol, and the isocyanate employed inpolymerization, and, as needed, other polymerization components,including chain-extending agents. From the perspective of controllingthe reaction rate, the mixture or solution composition of the presentinvention is desirably subjected to the urethane-forming reaction withthe isocyanate compound after the addition of the catalyst thereto.

The mixture or solution composition of the present invention, polyol,and polyisocyanate are desirably dissolved in solvent (polymerizationsolvent) and polymerized while conducting heating, pressurization,nitrogen substitution, and the like as needed. The solvent employed canbe selected from among known solvents employed in the synthesis ofpolyurethane resin. Examples are: ketone-based solvents such as acetone,methyl ethyl ketone, and cyclohexanone; ester-based solvents such asmethyl acetate, ethyl acetate, and ethyl lactate; ether-based solventssuch as dioxane and tetrahydrofuran; aromatic solvents such as tolueneand xylene; amide-based solvents such as N,N-dimethyl formamide,N,N-dimethyl acetamide, and N-methyl pyrrolidone; sulfoxide solventssuch as dimethyl sulfoxide; methylene chloride; chloroform; andcyclohexanone. Of these, methyl ethyl ketone and cyclohexanone aresuitably employed.

The weight average molecular weight of the polyurethane resin of thepresent invention is desirably equal to or greater than 10,000 but equalto or lower than 200,000 (in the present invention, the phrase “equal toor greater than 10,000 but equal to or lower than 200,000” may also bestated as “10,000 to 200,000”; identical below), preferably 40,000 to100,000, and more preferably, 50,000 to 90,000. A weight averagemolecular weight of the polyurethane resin of equal to or greater than10,000 is desirable in that good storage properties can be achieved, anddesirably equal to or lower than 200,000 because powders can dispersewell.

Examples of methods that can be used to keep the weight averagemolecular weight within the above-stated range are given below.

By way of example, the weight average molecular weight can be adjustedby slightly adjusting the mole ratio of glycol-derived OH groups todiisocyanate-derived NCO groups, and by employing a reaction catalyst.

Examples of reaction catalysts are: organic metal oxides such asdibutyltin dilaurate; tertiary amines such as triethylamine andtriethylene diamine; and metal salts such as potassium acetate and zincstearate. Dibutyltin dilaurate is a desirable example.

Other methods of adjusting the weight average molecular weight includeadjusting the solid component concentration, reaction temperature,reaction catalyst, reaction time, and the like during the reaction.

The molecular weight distribution (Mw/Mn) of the polyurethane resin isdesirably 1.0 to 2.5, preferably 1.5 to 2.0. A molecular weightdistribution of equal to or lower than 2.5 is desirable in that gooddispersion can be achieved with a low composition distribution.

As stated above, the urethane group concentration in the polyurethaneresin of the present invention is desirably 2.5 to 4.5 mmol/g,preferably 3.0 to 4.0 mmol/g. A urethane group concentration of equal toor higher than 2.5 mmol/g is desirable in that good durability can beachieved without decreasing the Tg of the coating containing thepolyurethane resin of the present invention as a binder component. Aconcentration of equal to or higher than 4.5 mmol/g is desirable in thatgood solvent solubility can be achieved and good dispersion propertiescan be obtained, facilitating control of the molecular weight.

The glass transition temperature (Tg) of the polyurethane resin of thepresent invention is desirably 80 to 200° C., preferably 90 to 160° C. Aglass transition temperature of equal to or higher than 80° C. isdesirable in that a film of high strength can be formed and durabilityand storage properties can be enhanced. A glass transition temperatureof equal to or higher than 200° C. is desirable in that a coating withgood calendering moldability can be obtained and a magnetic recordingmedium of good electromagnetic characteristics can be formed.

Further, the glass transition temperature (Tg) of the radiation-curablepolyurethane resin is desirably 10 to 160° C., preferably 10 to 100° C.A glass transition temperature of equal to or higher than 10° C. isdesirable in that good coating strength can be achieved following curingwith radiation, and durability and storage properties can be enhanced. Aglass transition temperature of equal to or higher than 160° C. isdesirable in that calendering moldability can be good even whencalendering is conducted after curing with radiation, and a magneticrecording medium with good electromagnetic characteristics can beformed.

The polar group content is desirably from 1×10⁻⁵ to 2×10⁻³ eq/g,preferably from 1×10⁻⁵ to 1×10⁻³ eq/g, and more preferably, from 1×10⁻⁵to 5×10⁻⁴ eq/g. A polar group content of equal to or greater than 1×10⁻⁵eq/g is desirable in that adequate adsorptive strength to powder can beachieved and dispersion can be good. A polar group content of equal toor lower than 2×10⁻³ eq/g is desirable in that good solubility insolvent can be achieved.

Since the compound denoted by general formula (1) can be employed as apolyol in the polyurethane resin of the present invention, it has apolar group in the form of —SO₃M. In this context, M is defined asabove.

The polyurethane resin of the present invention may further compriseother polar groups.

Other polar groups in the form of —OSO₃M, —PO₃M₂, and —COOM aredesirable. Of these, —OSO₃M is preferred. M denotes a hydrogen atom or amonovalent cation. Examples of monovalent cations are alkali metals andammonium.

A hydroxyl (OH) group can be contained in the polyurethane resin of thepresent invention. Two to twenty OH groups per molecule are desirableand 3 to 15 are preferred. When the number of OH groups desirably fallswithin this range, the coating strength and durability can be enhanceddue to enhanced reactivity with the isocyanate curing agent, anddispersion can be good due to enhanced solubility in solvent.

Acrylic double bonds can be incorporated into the polyurethane resin ofthe present invention by using a diol having at least one acrylic doublebond per molecule.

The content of double bonds (ethylenic unsaturated bonds) is desirablyfrom 1×10⁻⁵ to 2×10⁻³ eq/g, preferably 1×10⁻⁵ to 1×10⁻³ eq/g, and morepreferably, 1×10⁻⁴ to 1×10⁻³ eq/g.

A double bond content of equal to or greater than 1×10⁻⁵ eq/g isdesirable in that good coating strength can be achieved following curingwith radiation. A double bond content of equal to or lower than 2×10⁻³eq/g is desirable in that calendering moldability can be good even whencalendering is conducted after curing with radiation, and a magneticrecording medium with good electromagnetic characteristics can beformed.

Method of Manufacturing Polyurethane Resin

In the method of manufacturing polyurethane resin of the presentinvention, the mixture or solution composition of the present inventionis subjected to a urethane producing reaction with an isocyanatecompound. The details thereof are as set forth above.

Magnetic Recording Medium

The present invention relates to a magnetic recording medium comprisinga magnetic layer comprising a ferromagnetic powder and a binder on anonmagnetic support (referred to as “Medium 1” hereinafter), and amagnetic recording medium comprising a nonmagnetic layer comprising anonmagnetic powder and a binder and a magnetic layer comprising aferromagnetic powder and a binder in this order on a nonmagnetic support(referred to as “Medium 2” hereinafter).

In Medium 1, the binder comprised in the magnetic layer comprises thepolyurethane resin of the present invention. In Medium 2, the bindercomprised in the magnetic layer and/or the binder comprised in thenonmagnetic layer comprises the polyurethane resin of the presentinvention.

Medium 1 and Medium 2 will be collectively referred to as “the magneticrecording medium of the present invention” hereinafter.

The magnetic recording medium of the present invention will be describedin greater detail below.

(Binder)

The magnetic recording medium of the present invention comprises thepolyurethane resin of the present invention as the binder in themagnetic layer and/or nonmagnetic layer. In addition to the polyurethaneresin of the present invention, binder components may be incorporated inthe form of known thermoplastic resins, thermosetting resins, andreactive resins. Examples of thermoplastic resins are: polymers andcopolymers containing structural units such as vinyl chloride, vinylacetate, vinyl alcohol, maleic acid, acrylic acid, acrylic acid ester,vinylidene chloride, acrylonitrile, methacrylic acid, methacrylic acidester, styrene, butadiene, ethylene, vinyl butyral, vinyl acetal, andvinyl ether; and various rubber-based resins. Examples of thermosettingresins and reactive resins are: phenol resins, epoxy resins,polyurethane-cured resins, urea resins, melamine resins, alkyd resins,acrylic reaction resins, formaldehyde resins, silicone resins,epoxy-polyamide resins, mixtures of polyester resins and isocyanatepolymers, mixtures of polyester polyols and polyisocyanates, andmixtures of polyurethanes and polyisocyanates. These resins aredescribed in detail in the “Plastics Handbook” published by AsakuraShoten, which is expressly incorporated herein by reference in itsentirety. Known electron-beam curable resins can also be employed in thevarious layers. These examples and methods for preparing them aredescribed in detail in Japanese Unexamined Patent Publication (KOKAI)Showa No. 62-256219, which is expressly incorporated herein by referencein its entirety. The above resins may be employed singly or incombination.

In the magnetic recording medium, a thermosetting compound is normallyemployed as a curing agent (also referred to as a crosslinking agent) tocrosslink and cure the binder resin and increase the coating strength.Polyisocyanates are widely employed as curing agents. The polyisocyanateis desirably in the form of a trifunctional or greater polyisocyanate.Specific examples are adduct polyisocyanate compounds such as thecompound obtained by adding three moles of trilene diisocyanate (TDI) totrimethylol propane (TMP); the compound obtained by adding three molesof hexamethylene diisocyanate (HDI) to TMP; the compound obtained byadding three moles of isophorone diisocyanate (IPDI) to TMP; thecompound obtained by adding three moles of xylylene diisocyanate (XDI)to TMP; condensation isocyanurate trimers of TDI, condensationisocyanurate pentamers of TDI, condensation isocyanurate heptamers ofTDI, and mixtures thereof; isocyanurate condensates of HDI andisocyanurate condensates of IPDI; and crude MDI. Of these, compoundsobtained by adding three moles of TDI to TMP and isocyanurate trimers ofTDI are desirable.

Curing agents that are curable with radiation such as electron beams andultraviolet radiation can be employed in addition to isocyanate curingagents. A curing agent having two or more, desirably three or more,radiation curable functional groups in the form of acryloyl groups ormethacryloyl groups within the molecule is desirably employed. Examplesare trimethylol propane (TMP) triacrylate, pentaerythritoltetraacrylate, and urethane acrylate oligomers. In this case,(meth)acryloyl groups are desirably incorporated into the binder inaddition to a curing agent. For ultraviolet curing, a photosensitizingagent can be additionally employed.

From the perspective of maintaining dispersibility, the curing agent isdesirably added in a proportion of equal to or more than 0 weight partbut equal to or less than 80 weight parts per 100 weight parts of binderexcluding the curing agent.

Binder is employed, for example, within a range of 5 to 50 weightpercent, desirably within a range of 10 to 30 weight percent, of thenonmagnetic powder or ferromagnetic powder in the nonmagnetic layer ormagnetic layer. The quantity of polyurethane resin of the presentinvention that is employed is desirably equal to or greater than 50weight percent, preferably 60 to 100 weight percent, and morepreferably, 70 to 100 weight percent, of the total binder. The contentof the polyurethane resin of the present invention in the binderdesirably falls within this range to achieve good dispersion.

(Magnetic Layer)

The magnetic layer comprises a ferromagnetic powder in addition to thebinder.

The average particle size of the ferromagnetic powder can be measured bythe following method.

Particles of ferromagnetic powder are photographed at a magnification of100,000-fold with a model H-9000 transmission electron microscope madeby Hitachi and printed on photographic paper at a total magnification of500.000-fold to obtain particle photographs. The targeted magneticmaterial is selected from the particle photographs, the contours of thepowder material are traced with a digitizer, and the size of theparticles is measured with KS-400 image analyzer software from CarlZeiss. The size of 500 particles is measured. The average value of theparticle sizes measured by the above method is adopted as an averageparticle size of the ferromagnetic powder.

The size of a powder such as the magnetic material (referred to as the“powder size” hereinafter) in the present invention is denoted: (1) bythe length of the major axis constituting the powder, that is, the majoraxis length, when the powder is acicular, spindle-shaped, or columnar inshape (and the height is greater than the maximum major diameter of thebottom surface); (2) by the maximum major diameter of the tabularsurface or bottom surface when the powder is tabular or columnar inshape (and the thickness or height is smaller than the maximum majordiameter of the tabular surface or bottom surface); and (3) by thediameter of an equivalent circle when the powder is spherical,polyhedral, or of unspecified shape and the major axis constituting thepowder cannot be specified based on shape. The “diameter of anequivalent circle” refers to that obtained by the circular projectionmethod.

The average powder size of the powder is the arithmetic average of theabove powder size and is calculated by measuring five hundred primaryparticles in the above-described method. The term “primary particle”refers to a nonaggregated, independent particle.

The average acicular ratio of the powder refers to the arithmeticaverage of the value of the (major axis length/minor axis length) ofeach powder, obtained by measuring the length of the minor axis of thepowder in the above measurement, that is, the minor axis length. Theterm “minor axis length” means the length of the minor axis constitutinga powder for a powder size of definition (1) above, and refers to thethickness or height for definition (2) above. For (3) above, the (majoraxis length/minor axis length) can be deemed for the sake of convenienceto be 1, since there is no difference between the major and minor axes.

When the shape of the powder is specified, for example, as in powdersize definition (1) above, the average powder size refers to the averagemajor axis length. For definition (2) above, the average powder sizerefers to the average plate diameter, with the arithmetic average of(maximum major diameter/thickness or height) being referred to as theaverage plate ratio. For definition (3), the average powder size refersto the average diameter (also called the average particle diameter). Inthe measurement of powder size, the standard deviation/average value,expressed as a percentage, is defined as the coefficient of variation.

Acicular ferromagnetic powder, platelike magnetic powder, sphericalmagnetic powder, or elliptical magnetic powder can be employed as theferromagnetic powder. Each of these will be described below.

(1) Acicular Ferromagnetic Powder

Examples of acicular ferromagnetic powders that can be employed as theferromagnetic powder employed in the magnetic recording medium of thepresent invention are ferromagnetic metal powders such as acicularcobalt-containing ferromagnetic iron oxide and ferromagnetic alloypowders. The BET specific surface area (S_(BET)) of these powders isdesirably equal to or greater than 40 m²/g but equal to or lower than 80m²/g, preferably equal to or greater than 50 m²/g but equal to or lowerthan 70 m²/g. The crystallite size is desirably equal to or greater than8 nm but equal to or lower than 25 nm, preferably equal to or greaterthan 9 nm but equal to or lower than 22 nm, and more preferably, equalto or greater than 10 nm but equal to or lower than 20 nm. The majoraxis length is desirably equal to or greater than 20 nm but equal to orlower than 50 nm and preferably equal to or greater than 20 nm but equalto or lower than 45 nm.

Examples of ferromagnetic powders are ferromagnetic metal powders suchas yttrium-containing Fe, Fe—Co, Fe—Ni, and Co—Ni—Fe. The yttriumcontent of the ferromagnetic powder is desirably equal to or greaterthan 0.5 atomic percent but equal to or less than 20 atomic percent,preferably equal to or greater than 5 atomic percent but equal to orless than 10 atomic percent, as the ratio Y/Fe of yttrium atoms to ironatoms. A ratio of 0.5 atomic percent or greater is desirable in that ahigh as value can be achieved in the ferromagnetic powder, good magneticcharacteristics can be obtained, and good electromagneticcharacteristics can be attained. A ratio of 20 atomic percent or loweris desirable in that the iron content is suitable, good magneticcharacteristics can be obtained, and good electromagneticcharacteristics can be attained. Within a range of equal to or less than20 atomic percent per 100 atomic percent of iron, it is possible toincorporate aluminum, silicon, sulfur, scandium, titanium, vanadium,chromium, manganese, copper, zinc, molybdenum, rhodium, palladium, tin,antimony, boron, barium, tantalum, tungsten, rhenium, gold, lead,phosphorus, lanthanum, cerium, praseodymium, neodymium, tellurium,bismuth, and the like. The ferromagnetic metal powder may contain smallquantities of water, hydroxides, or oxides.

An example of a method of manufacturing ferromagnetic powder in whichcobalt or yttrium is incorporated that can be employed as theferromagnetic powder will be described.

One example is to blow an oxidizing gas into an aqueous suspension offerrous salt and an alkali to obtain iron oxyhydroxide, which is thenused as a starting material.

The iron oxyhydroxide is desirably α-FeOOH. A first manufacturing methodis to neutralize ferrous salt with an alkali hydroxide to obtain anaqueous suspension of Fe(OH)₂. An oxidizing gas is then blown into thesuspension to obtain acicular-shaped α-FeOOH. A second manufacturingmethod is to neutralize ferrous salt with alkali carbonate to obtain anaqueous suspension of FeCO₃. An oxidizing gas is then blown into thesuspension to obtain spindle-shaped α-FeOOH. Such iron oxyhydroxides aredesirably obtained by reacting an aqueous solution of ferrous salt withan aqueous solution of an alkali to obtain an aqueous solutioncontaining ferrous hydroxide. This aqueous solution is then oxidized byoxidation with air or the like. In this process, alkaline earth elementsalts such as Ni salt, Ca salt, Ba salt, and Sr salt, as well as Crsalt, Zn salt, and the like may be present in the ferrous salt aqueoussolution. The particle shape (axial ratio) and the like may be adjustedby suitably selecting such salts.

Ferrous chloride, ferrous sulfate, and the like are desirable as theferrous salt. Sodium hydroxide, ammonia water, ammonium carbonate,sodium carbonate, and the like are desirable as the alkali. Chloridessuch as nickel chloride, calcium chloride, barium chloride, strontiumchloride, chromium chloride, and zinc chloride are desirable as thesalts that can be additionally present.

When incorporating cobalt onto iron, before incorporating yttrium, anaqueous solution of a cobalt compound such as cobalt sulfate or cobaltchloride is admixed to a slurry of the above-described ferrousoxyhydroxide. Once a slurry of iron oxyhydroxide containing cobalt hasbeen prepared, an aqueous solution containing an yttrium compound isadded to the slurry and stirred to complete the incorporation.

In addition to yttrium, it is possible to incorporate neodymium,samarium, praseodymium, lanthanum, gadolinium, and the like into theferromagnetic powder. These can be incorporated using chlorides such asyttrium chloride, neodymium chloride, samarium chloride, praseodymiumchloride, and lanthanum chloride; nitrates such as neodymium nitrate andgadolinium nitrate; and the like. Two or more of these may be employedin combination.

The coercivity (Hc) of the ferromagnetic metal powder is desirably equalto or greater than 159.2 kA/m but equal to or lower than 238.8 kA/m(equal to or greater than 2,000 Oe equal to or lower than 3,000 Oe),preferably equal to or greater than 1.67.2 kA/m but equal to or lowerthan 230.8 kA/m (equal to or greater than 2,100 Oe but equal to or lowerthan 2,900 Oe).

Further, the saturation flux density is desirably equal to or greaterthan 150 mT but equal to or lower than 300 mT (equal to or greater than1,500 G but equal to or lower than 3,000 G), preferably equal to orgreater than 160 mT but equal to or lower than 290 mT (equal to orgreater than 600 G but equal to or lower than 2,900 G). The saturationmagnetization (as) is desirably equal to or greater than 100 A·m²/kg butequal to or lower than 170 A·m²/kg (equal to or greater than 100 emu/gbut equal to or lower than 170 emu/g), preferably equal to or greaterthan 110 A·m²/kg but equal to or lower than 160 A·m²/kg (equal to orgreater than 110 emu/g but equal to or lower than 160 emu/g).

The lower the switching field distribution (SFD) of the magnetic powderitself, the better: equal to or lower than 0.8 is desirable. At an SFDof 0.8 or lower, electromagnetic characteristics can be good, output canbe high, and magnetic reversal can be sharp with little peak shift. Sucha level is suited to high-density digital recording. Methods of loweringthe Hc distribution include improving the particle size distribution ofgoethite in the ferromagnetic metal powder, employing monodispersedα-Fe₂O₃, and preventing sintering between particles.

(2) Platelike Magnetic Powder

Hexagonal ferrite powder is desirable as a platelike magnetic powderemployed as ferromagnetic powder.

Examples of hexagonal ferrite powders are barium ferrite, strontiumferrite, lead ferrite, calcium ferrite, and various substitutionproducts thereof such as Co substitution products. Specific examples aremagnetoplumbite-type barium ferrite and strontium ferrite;magnetoplumbite-type ferrite in which the particle surfaces are coveredwith spinels; and magnetoplumbite-type barium ferrite, strontiumferrite, and the like partly comprising a spinel phase. The followingmay be incorporated into the hexagonal ferrite powder in addition to theprescribed atoms: Al, Si, S, Sc, Ti, V, Cr, Cu, Y, Mo, Rh, Pd, Ag, Sn,Sb, Te, Ba, Ta, W, Re, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, P, Co, Mn, Zn,Ni, Sr, B, Ge, Nb, Zr, Zn and the like. Compounds to which elements suchas Co—Zn, Co—Ti, Co—Ti—Zr, Co—Ti—Zn, Ni—Ti—Zn, Nb—Zn—Co, Sb—Zn—Co, andNb—Zn have been added may generally also be employed. They may comprisespecific impurities depending on the starting materials andmanufacturing methods employed.

The particle size is preferably equal to or greater than 10 nm but equalto or less than 50 nm as a hexagonal plate diameter. When employing amagnetoresistive head in reproduction, a plate diameter equal to or lessthan 40 nm is desirable to reduce noise. A plate diameter within theabove range can yield stable magnetization without the effects ofthermal fluctuation, and permit low noise, that is suited to thehigh-density magnetic recording.

The plate ratio (plate diameter/plate thickness) is preferably equal toor greater than 1 but equal to or lower than 15, more preferably equalto or greater than 2 but equal to or lower than 7. Within the aboverange, adequate orientation can be achieved and noise can be decreaseddue to prevention of stacking between particles. The specific surfacearea by BET method of the hexagonal ferrite powders having such particlesizes normally ranges from 10 to 200 m²/g, almost corresponding to anarithmetic value from the particle plate diameter and the platethickness. Narrow distributions of particle plate diameter and thicknessare normally good. Although difficult to render in number form, about500 particles can be randomly measured in a transmission electronmicroscope (TEM) photograph of particles to make a comparison. Thisdistribution is often not a normal distribution. However, when thedistribution is expressed as the standard deviation a to the averageparticle size, a/average particle size=0.1 to 2.0. The particleproducing reaction system is rendered as uniform as possible and theparticles produced are subjected to a distribution-enhancing treatmentto achieve a narrow particle size distribution. For example, methodssuch as selectively dissolving ultrafine particles in an acid solutionby dissolution are known.

A coercivity (Hc) of the hexagonal ferrite powder of about 500 to 5,000Oe (about 39.8 to 398 kA/m) can normally be achieved. A high coercivity(Hc) is advantageous for high-density recording, but this is limited bythe capacity of the recording head. The hexagonal ferrite powderemployed in the present invention preferably has a coercivity (Hc)ranging from 800 to 4,000 Oe (about 63.7 to 318.4 kA/m), more preferably1,500 to 3,500 Oe (about 119.4 to 278.6 kA/m). When the saturationmagnetization of the head exceeds 1.4 tesla, the hexagonal ferritehaving a coercivity (Hc) of equal to or higher than 2,200 Oe (aboutequal to or higher than 159.2 kA/m) is preferably employed.

The coercivity (Hc) can be controlled by particle size (plate diameterand plate thickness), the types and quantities of elements contained,substitution sites of the element, the particle producing reactionconditions, and the like. The saturation magnetization (σ_(s)) can be 40to 80 A·m²/kg (40 to 80 emu/g). The higher saturation magnetization(σ_(s)) is preferred, however, it tends to decrease with decreasingparticle size. Known methods of improving saturation magnetization(σ_(s)) are combining spinel ferrite with magnetoplumbite ferrite,selection of the type and quantity of elements incorporated, and thelike. It is also possible to employ W-type hexagonal ferrite.

When dispersing the hexagonal ferrite powder, the surface of thehexagonal ferrite powder can be processed with a substance suited to adispersion medium and a polymer. Both organic and inorganic compoundscan be employed as surface treatment agents. Examples of the principalcompounds are oxides and hydroxides of Si, Al, P, and the like; varioussilane coupling agents; and various titanium coupling agents. Thequantity of surface treatment agent added can range from 0.1 to 10weight percent relative to the weight of the hexagonal ferrite powder.The pH of the hexagonal ferrite powder can also be important todispersion. A pH of about 4 to 12 is usually optimum for the dispersionmedium and polymer. From the perspective of the chemical stability andstorage properties of the medium, a pH of about 6 to 10 can be selected.Moisture contained in the hexagonal ferrite powder also affectsdispersion. There is an optimum level for the dispersion medium andpolymer, usually selected from the range of 0.01 to 2.0 weight percent.

Methods of manufacturing the hexagonal ferrite powder include: (1) avitrified crystallization method consisting of mixing into a desiredferrite composition barium oxide, iron oxide, and a metal oxidesubstituting for iron with a glass forming substance such as boronoxide; melting the mixture; rapidly cooling the mixture to obtain anamorphous material; reheating the amorphous material; and refining andcomminuting the product to obtain a barium ferrite crystal powder; (2) ahydrothermal reaction method consisting of neutralizing a barium ferritecomposition metal salt solution with an alkali; removing the by-product;heating the liquid phase to 100° C. or greater; and washing, drying, andcomminuting the product to obtain barium ferrite crystal powder; and (3)a coprecipitation method consisting of neutralizing a barium ferritecomposition metal salt solution with an alkali; removing the by-product;drying the product and processing it at equal to or less than 1,100° C.;and comminuting the product to obtain barium ferrite crystal powder.However, any manufacturing method can be selected in the presentinvention.

(3) Spherical and Elliptical Magnetic Powder

An iron nitride-based ferromagnetic powder with Fe₁₆N₂ as the primaryphase is desirable as a spherical or elliptical magnetic powder. In theiron nitride-based ferromagnetic powder, atoms such as Al, Si, S, Sc,Ti, V, Cr, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, W, Re, Au, Hg, Pb,Bi, La, Ce, Pr, Nd, P, Co, Mn, Zn, Ni, Sr, B, Ge, and Nb can beincorporated in addition to Fe and N atoms. The content of N relative toFe is desirably equal to or greater than 1.0 atomic percent, but equalto or less than 20.0 atomic percent.

A spherical or elliptical shape is desirable for iron nitride, with anaxial ratio of the major axis diameter/minor axis diameter of equal toor greater than 1 but equal to or lower than 2 being desirable. The BETspecific surface area (S_(BET)) is desirably equal to or greater than 30m²/g but equal to or lower than 100 m²/g, preferably equal to or greaterthan 50 m²/g but equal to or lower than 70 m²/g. The crystallite size isdesirably equal to or greater than 12 nm but equal to or lower than 25nm, preferably equal to or greater than 13 nm but equal to or lower than22 nm.

The saturation magnetization σ_(s) is desirably equal to or greater than50 A·m²/kg (50 emu/g) but equal to or lower than 200 A·m²/kg (200emu/g), preferably equal to or greater than 70 A·m²/kg (70 emu/g) butequal to or lower than 150 A·m²/kg (150 emu/g).

(Nonmagnetic Layer)

Medium 2 comprises a nonmagnetic layer comprising a nonmagnetic powderand a binder between a nonmagnetic support and a magnetic layer. Thebinder in the magnetic layer and/or nonmagnetic layer comprises theabove-described polyurethane.

The nonmagnetic powder employed in the nonmagnetic layer can be anorganic or inorganic substance. Examples of inorganic substances are:metals, metal oxides, metal carbonates, metal sulfates, metal nitrides,metal carbides, and metal sulfides. Carbon black may also be employed.

Specifically, titanium oxides such as titanium dioxide, cerium oxide,tin oxide, tungsten oxide, ZnO, ZrO₂, SiO₂, Cr₂O₃, α-alumina with anα-conversion rate of 90 to 100 percent, β-alumina, γ-alumina, α-ironoxide, goethite, corundum, silicon nitride, titanium carbide, magnesiumoxide, boron nitride, molybdenum disulfide, copper oxide, MgCO₃, CaCO₃,BaCO₃, SrCO₃, BaSO₄, silicon carbide, and titanium carbide may beemployed singly or in combinations of two or more. α-iron oxide andtitanium oxide are preferred.

The nonmagnetic powder may be acicular, spherical, polyhedral, orplate-shaped.

The crystallite size of the nonmagnetic powder preferably ranges from 4nm to 1 μm, more preferably from 40 to 100 nm. The crystallite sizewithin 4 nm to 1 μm can achieve good dispersibility and suitable surfaceroughness.

The average particle diameter of the nonmagnetic powder preferablyranges from 5 nm to 2 μm. As needed, nonmagnetic powders of differingaverage particle diameter may be combined; the same effect may beachieved by broadening the average particle distribution of a singlenonmagnetic powder. The particularly preferred average particle diameterof the nonmagnetic powder ranges from 10 to 200 nm. Within a range of 5nm to 2 μm, dispersion can be good and good surface roughness can beachieved; the above range is preferred.

The specific surface area of the nonmagnetic powder desirably rangesfrom 1 to 100 m²/g, preferably from 5 to 70 m²/g, and more preferablyfrom 10 to 65 m²/g. Within the specific surface area ranging from 1 to100 m²/g, suitable surface roughness can be achieved and dispersion ispossible with the desired quantity of binder; the above range ispreferred.

Oil absorption capacity using dibutyl phthalate (DBP) preferably rangesfrom 5 to 100 mL/100 g, more preferably from 10 to 80 mL/100 g, andfurther preferably from 20 to 60 mL/100 g.

The specific gravity desirably ranges from 1 to 12, preferably from 3 to6. The tap density desirably ranges from 0.05 to 2 g/mL, preferably from0.2 to 1.5 g/mL. A tap density falling within a range of 0.05 to 2 g/mLcan reduce the amount of scattering particles, thereby facilitatinghandling, and tends to prevent solidification to the device.

The pH of the nonmagnetic powder preferably ranges from 2 to 11, morepreferably from 6 to 9. When the pH falls within a range of 2 to 11, thecoefficient of friction does not become high at high temperature or highhumidity or due to the freeing of fatty acids.

The moisture content of the nonmagnetic powder desirably ranges from 0.1to 5 weight percent, preferably from 0.2 to 3 weight percent, and morepreferably from 0.3 to 1.5 weight percent. A moisture content fallingwithin a range of 0.1 to 5 weight percent is desirable because it canproduce good dispersion and yield a stable coating viscosity followingdispersion. An ignition loss of equal to or less than 20 weight percentis desirable and nonmagnetic powders with low ignition losses aredesirable.

When the nonmagnetic powder is an inorganic powder, the Mohs' hardnessis preferably 4 to 10. Durability can be ensured if the Mohs' hardnessranges from 4 to 10. The stearic acid (SA) adsorption capacity of thenonmagnetic powder preferably ranges from 1 to 20 μmol/m², morepreferably from 2 to 15 μmol/m². The heat of wetting in 25° C. water ofthe nonmagnetic powder is preferably within a range of 200 to 600erg/cm² (20 to 60 μJ/cm²). A solvent with a heat of wetting within thisrange may also be employed. The quantity of water molecules on thesurface at 100 to 400° C. suitably ranges from 1 to 10 pieces per 100Angstroms. The pH of the isoelectric point in water preferably rangesfrom 3 to 9.

The surface of these nonmagnetic powders preferably contains Al₂O₃,SiO₂, TiO₂, ZrO₂, SnO₂, Sb₂O₃, and ZnO by conducting surface treatment.The surface-treating agents of preference with regard to dispersibilityare Al₂O₃, SiO₂, TiO₂, and ZrO₂, and Al₂O₃, SiO₂ and ZrO₂ are furtherpreferable. They may be employed singly or in combination. Depending onthe objective, a surface-treatment coating layer with a coprecipitatedmaterial may also be employed, the method which comprises a firstalumina coating and a second silica coating thereover or the reversemethod thereof may also be adopted. Depending on the objective, thesurface-treatment coating layer may be a porous layer, with homogeneityand density being generally desirable.

Specific examples of nonmagnetic powders suitable for use in thenonmagnetic layer are: Nanotite from Showa Denko K. K.; HIT-100 andZA-G1 from Sumitomo Chemical Co., Ltd.; DPN-250, DPN-250BX, DPN-245,DPN-270BX, DPN-550BX and DPN-550RX from Toda Kogyo Corp.; titanium oxideTTO-51B, TTO-55A, TTO-55B, TTO-55C, TTO-55S, TTO-55D, SN-100, MJ-7,α-iron oxide E270, E271 and E300 from Ishihara Sangyo Co., Ltd.; STT-4D,STT-30D, STT-30 and STT-65C from Titan Kogyo K. K.; MT-100S, MT-100T,MT-150W, MT-500B, T-600B, T-100F and T-500HD from Tayca Corporation;FINEX-25, BF-1, BF-10, BF-20 and ST-M from Sakai Chemical Industry Co.,Ltd.; DEFIC-Y and DEFIC-R from Dowa Mining Co., Ltd.; AS2BM and TiO2P25from Nippon Aerogil; 100A and 500A from Ube Industries, Ltd.; Y-LOP fromTitan Kogyo K. K.; and sintered products of the same. Particularpreferable nonmagnetic powders are titanium dioxide and α-iron oxide.

Based on the objective, an organic powder may be added to thenonmagnetic layer. Examples of such an organic powder are acrylicstyrene resin powders, benzoguanamine resin powders, melamine resinpowders, and phthalocyanine pigments. Polyolefin resin powders,polyester resin powders, polyamide resin powders, polyimide resinpowders, and polyfluoroethylene resins may also be employed. Themanufacturing methods described in Japanese Unexamined PatentPublication (KOKAI) Showa Nos. 62-18564 and 60-255827 may be employed.The contents of the above publications are expressly incorporated hereinby reference in their entirety.

(Carbon Black)

The magnetic recording medium of the present invention can comprisecarbon black in the magnetic layer and/or nonmagnetic layer. Examples oftypes of carbon black that are suitable for use are: furnace black forrubber, thermal for rubber, black for coloring and acetylene black. Aspecific surface area of 5 to 500 m²/g, a DBP oil absorption capacity of10 to 400 ml/100 g, and an average particle size of 5 to 300 nm,preferably 10 to 250 nm, more preferably 20 to 200 nm are respectivelydesirable. A pH of 2 to 10, a moisture content of 0.1 to 10 percent, anda tap density of 0.1 to 1 g/cc are respectively desirable. Specificexamples of types of carbon black employed are: BLACK PEARLS 2000, 1300,1000, 900, 905, 800, 700 and VULCAN XC-72 from Cabot Corporation; #80,#60, #55, #50 and #35 manufactured by Asahi Carbon Co., Ltd.; #2400B,#2300, #900, #1000, #30, #40 and #10B from Mitsubishi ChemicalCorporation; CONDUCTEX SC, RAVEN 150, 50, 40, 15 and RAVEN MT-P fromColumbia Carbon Co., Ltd.; and Ketjen Black EC from Lion Akzo Co., Ltd.The carbon black employed may be surface-treated with a dispersant orgrafted with resin, or have a partially graphite-treated surface. Thecarbon black may be dispersed in advance into the binder prior toaddition to the coating liquid. These carbon blacks may be used singlyor in combination. The quantity of carbon black preferably ranges from0.1 to 30 weight percent relative to the ferromagnetic powder ornonmagnetic powder, when carbon black is employed. In the magneticlayer, carbon black can work to prevent static, reduce the coefficientof friction (impart smoothness), impart light-blocking properties,enhance film strength, and the like; the properties vary with the typeof carbon black employed. Carbon black can be mixed into the nonmagneticlayer to achieve the known effect of reducing surface resistivity Rs andoptical transmittance, and achieving a desired micro-Vicker's hardness.A lubricant stockpiling effect can also be achieved by incorporatingcarbon black into the nonmagnetic layer. Accordingly, based oncharacteristics required for the magnetic layer and nonmagnetic layer,different types of carbon black can be employed in the magnetic layerand nonmagnetic layer in light of various characteristics such as types,quantities, particle size, oil absorption capacity, electricalconductivity, and pH. The carbon black is preferably optimized for eachlayer. For example, Carbon Black Handbook compiled by the Carbon BlackAssociation, which is expressly incorporated herein by reference in itsentirety, may be consulted for types of carbon black suitable for use inthe magnetic layer and/or nonmagnetic layer.

(Abrasives)

Known materials chiefly having a Mohs' hardness of 6 or greater may beemployed either singly or in combination as abrasives in the presentinvention. These include: α-alumina with an α-conversion rate of equalto or greater than 90 percent, β-alumina, silicon carbide, chromiumoxide, cerium oxide, α-iron oxide, corundum, synthetic diamond, siliconnitride, silicon carbide, titanium carbide, titanium oxide, silicondioxide, and boron nitride. Complexes of these abrasives (obtained bysurface treating one abrasive with another) may also be employed. Thereare cases in which compounds or elements other than the primary compoundare contained in these abrasives; the effect does not change so long asthe content of the primary compound is equal to or greater than 90weight percent. The average particle size of the abrasive is preferably0.01 to 2 micrometers, more preferably 0.05 to 1.0 micrometer, andfurther preferably, 0.05 to 0.5 micrometer. To enhance electromagneticcharacteristics, a narrow particle size distribution is desirable.Abrasives of differing particle size may be incorporated as needed toimprove durability; the same effect can be achieved with a singleabrasive as with a wide particle size distribution. It is preferablethat the tap density is 0.3 to 2 g/cc, the moisture content is 0.1 to 5percent, the pH is 2 to 11, and the specific surface area is 1 to 30m²/g. The shape of the abrasive employed in the present invention may beacicular, spherical, cubic, or the like. However, a shape comprising anangular portion is desirable due to high abrasiveness. Specific examplesare AKP-12, AKP-15, AKP-20, AKP-30, AKP-50, HIT-20, HIT-30, HIT-55,HIT-60, HIT-70, HIT-80, and HIT-100 made by Sumitomo Chemical Co., Ltd.;ERC-DBM, HP-DBM, and HPS-DBM made by Reynolds Corp.; WA10000 made byFujimi Abrasive Corp.; UB20 made by Uemura Kogyo Corp.; G-5, Chromex U2,and Chromex U1 made by Nippon Chemical Industrial Co., Ltd.; TF100 andTF140 made by Toda Kogyo Corp.; Beta Random Ultrafine made by IbidenCo., Ltd.; and B-3 made by Showa Kogyo Co., Ltd. Abrasives may be addedas needed to the nonmagnetic layer. Addition of abrasives to thenonmagnetic layer can be done to control surface shape, control how theabrasive protrudes, and the like. The particle size and quantity of theabrasives added to the magnetic layer and nonmagnetic layer arepreferably set to optimal values.

(Additives)

Substances having lubricating effects, antistatic effects, dispersiveeffects, plasticizing effects, or the like may be employed as additivesin the magnetic layer and nonmagnetic layer. Examples of additives are:molybdenum disulfide; tungsten disulfide; graphite; boron nitride;graphite fluoride; silicone oils; silicones having a polar group; fattyacid-modified silicones; fluorine-containing silicones;fluorine-containing alcohols; fluorine-containing esters; polyolefins;polyglycols; alkylphosphoric esters and their alkali metal salts;alkylsulfuric esters and their alkali metal salts; polyphenyl ethers;phenylphosphonic acid; α-naphthylphosphoric acid; phenylphosphoric acid;diphenylphosphoric acid; p-ethylbenzenephosphonic acid; phenylphosphinicacid; aminoquinones; various silane coupling agents and titaniumcoupling agents; fluorine-containing alkylsulfuric acid esters and theiralkali metal salts; monobasic fatty acids (which may contain anunsaturated bond or be branched) having 10 to 24 carbon atoms and metalsalts (such as Li, Na, K, and Cu) thereof; monohydric, dihydric,trihydric, tetrahydric, pentahydric or hexahydric alcohols with 12 to 22carbon atoms (which may contain an unsaturated bond or be branched);alkoxy alcohols with 12 to 22 carbon atoms; monofatty esters, difattyesters, or trifatty esters comprising a monobasic fatty acid having 10to 24 carbon atoms (which may contain an unsaturated bond or bebranched) and any one from among a monohydric, dihydric, trihydric,tetrahydric, pentahydric or hexahydric alcohol having 2 to 12 carbonatoms (which may contain an unsaturated bond or be branched); fatty acidesters of monoalkyl ethers of alkylene oxide polymers; fatty acid amideswith 8 to 22 carbon atoms; and aliphatic amines with 8 to 22 carbonatoms.

Specific examples of the additives in the form of fatty acids are:capric acid, caprylic acid, lauric acid, myristic acid, palmitic acid,stearic acid, behenic acid, oleic acid, elaidic acid, linolic acid,linolenic acid, and isostearic acid. Examples of esters are butylstearate, octyl stearate, amyl stearate, isooctyl stearate, butylmyristate, octyl myristate, butoxyethyl stearate, butoxydiethylstearate, 2-ethylhexyl stearate, 2-octyldodecyl palmitate,2-hexyldodecyl palmitate, isohexadecyl stearate, oleyl oleate, dodecylstearate, tridecyl stearate, oleyl erucate, neopentylglycol didecanoate,and ethylene glycol dioleyl. Examples of alcohols are oleyl alcohol,stearyl alcohol, and lauryl alcohol. It is also possible to employnonionic surfactants such as alkylene oxide-based surfactants,glycerin-based surfactants, glycidol-based surfactants andalkylphenolethylene oxide adducts; cationic surfactants such as cyclicamines, ester amides, quaternary ammonium salts, hydantoin derivatives,heterocycles, phosphoniums, and sulfoniums; anionic surfactantscomprising acid groups, such as carboxylic acid, sulfonic acid,phosphoric acid, sulfuric ester groups, and phosphoric ester groups; andampholytic surfactants such as amino acids, amino sulfonic acids,sulfuric or phosphoric esters of amino alcohols, and alkyl betaines.Details of these surfactants are described in A Guide to Surfactants(published by Sangyo Tosho K.K.), which is expressly incorporated hereinby reference in its entirety. These lubricants, antistatic agents andthe like need not be 100 percent pure and may contain impurities, suchas isomers, unreacted material, by-products, decomposition products, andoxides in addition to the main components. These impurities arepreferably comprised equal to or less than 30 weight percent, and morepreferably equal to or less than 10 weight percent.

The lubricants and surfactants suitable for use in the present inventioneach have different physical effects. The type, quantity, andcombination ratio of lubricants producing synergistic effects can beoptimally set for a given objective. It is conceivable to controlbleeding onto the surface through the use of fatty acids havingdifferent melting points in the nonmagnetic layer and the magneticlayer; to control bleeding onto the surface through the use of estershaving different boiling points, melting points, and polarity; toimprove the stability of coatings by adjusting the quantity ofsurfactant; and to increase the lubricating effect by increasing theamount of lubricant in the intermediate layer. The present invention isnot limited to these examples. In general, the total amount of lubricantcan be 0.1 to 50 weight percent, and preferably 2 to 25 weight percentwith respect to the ferromagnetic powder or nonmagnetic powder.

Known organic solvents can be used. Examples of the organic solvents areketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone,diisobutyl ketone, cyclohexanone, isophorone, and tetrahydrofuran;alcohols such as methanol, ethanol, propanol, butanol, isobutyl alcohol,isopropyl alcohol, and methylcyclohexanol; esters such as methylacetate, butyl acetate, isobutyl acetate, isopropyl acetate, ethyllactate, and glycol acetate; glycol ethers such as glycol dimethylether, glycol monoethyl ether, and dioxane; aromatic hydrocarbons suchas benzene, toluene, xylene, cresol, and chlorobenzene; chlorinatedhydrocarbons such as methylene chloride, ethylene chloride, carbontetrachloride, chloroform, ethylene chlorohydrin, and dichlorobenzene;N,N-dimethylformamide; and hexane; these may be employed in any ratio.

All or a portion of the additives employed in the present invention canbe added during any step in the manufacturing of a magnetic layercoating liquid and nonmagnetic layer coating liquid. For example, thereare times when they are mixed with the ferromagnetic powder before thekneading step, times when they are added with the ferromagnetic powder,binder and solvent in the kneading step, times when they are addedduring the dispersing step, times when they are added after thedispersing step, and times when they are added immediately prior tocoating. Based on the objective, there are times when an objective isachieved by coating all or part of the additives in simultaneous orsuccessive coatings after coating the magnetic layer. Based on theobjective, there are times when a lubricant is coated to the magneticlayer surface after calendering or slitting has been completed. Knownorganic solvents can be employed in the present invention. For example,the solvents described in Japanese Unexamined Patent Publication (KOKAI)Showa No. 6-68453, which is expressly incorporated herein by referencein its entirety, can be employed.

(Layer Structure)

In the magnetic recording medium of the present invention, the thicknessof the nonmagnetic support ranges from, for example, 2 to 100 μm,preferably from 2 to 80 μm. For computer-use magnetic recording tapes,the nonmagnetic support having a thickness of 3.0 to 6.5 μm, preferably3.0 to 6.0 μm, more preferably 4.0 to 5.5 μm is suitably employed.

An undercoating layer can be provided between the nonmagnetic supportand nonmagnetic layer to enhance adhesion. The undercoating layer is,for example, 0.01 to 0.5 μm, desirably 0.02 to 0.5 μm, in thickness. Themagnetic recording medium of the present invention may be a disk-shapedmedium in which a nonmagnetic layer and a magnetic layer are provided onboth surfaces of the support, or a tape-shaped or disk-shaped medium inwhich they are provided only on one side thereof. In such cases, abackcoat layer may be provided on the opposite side from the side onwhich the nonmagnetic layer and magnetic layer are provided to achievethe effects of preventing charge buildup, correcting for curling, andthe like. The thickness of the backcoat layer is, for example, 0.1 to 4μm, desirably 0.3 to 2.0 μm. Known undercoating layers and the backcoatlayers can be employed.

The thickness of the nonmagnetic layer is normally 0.2 to 5.0 μm,preferably 0.3 to 3.0 μm, and further preferably, 0.4 to 2.0 μm.

The thickness of the magnetic layer is desirably optimized based on thesaturation magnetization of the head employed, the length of the headgap, and the recording signal band, and is preferably 30 to 150 nm, morepreferably 50 to 120 nm, and further preferably, 60 to 100 nm. Thethickness variation in the magnetic layer is preferably within ±50percent, more preferably within ±30 percent. At least one magnetic layeris sufficient. The magnetic layer may be divided into two or more layershaving different magnetic characteristics, and a known configurationrelating to multilayered magnetic layer may be applied.

(Backcoat Layer)

Generally, stronger repeat running properties are demanded of magneticrecording media (magnetic tapes) for use in recording computer data thanof audio and video tapes. To maintain such high running durability,carbon black and inorganic powder are desirably incorporated into abackcoat layer.

An example of an inorganic powder that can be added to the backcoatlayer is an inorganic powder with a Mohs' hardness of 5 to 9 and anaverage particle size of 80 to 250 nm. Examples of inorganic powdersthat can be employed are α-iron oxide, α-alumina, chromium oxide(Cr₂O₃), and TiO₂. Of these, the use of α-iron oxide and α-alumina isdesirable.

The carbon blacks that are commonly employed in magnetic recording mediacan be widely employed in the backcoat layer. For example, furnace blackfor rubber, thermal for rubber, black for coloring and acetylene blackcan be employed. To prevent the transfer of backcoat layernonuniformities to the magnetic layer, the average particle size of thecarbon black is desirably equal to or lower than 0.3 μm, preferably 0.01to 0.1 μm. The quantity of carbon black employed in the backcoat layeris desirably such that the optical transmission density (thetransmission level of a TR-927 made by Macbeth) falls within a range ofequal to or lower than 2.0.

The use of two carbon blacks of differing average particle size isadvantageous to improve running durability. In that case, thecombination of a first carbon black having an average particle sizefalling within a range of 0.01 to 0.04 μm and a second carbon blackhaving an average particle size falling within a range of 0.05 to 0.3 μmis desirable. The quantity of the second carbon black is suitably 0.1 to10 weight parts, desirably 0.3 to 3 weigh parts, per 100 weight parts ofthe inorganic powder and the first carbon black combined. The quantityof binder employed can be selected within a range of 10 to 40 weightparts, preferably 20 to 32 weight parts, per 100 weight parts of theinorganic powder and carbon black combined. Conventionally knownthermoplastic resins, thermosetting resins, reactive resins, and thelike can be employed as the binder in the backcoat layer.

(Nonmagnetic Support)

Known films of the following may be employed as the nonmagnetic support:polyethylene terephthalate, polyethylene naphthalate, other polyesters,polyolefins, cellulose triacetate, polycarbonate, polyamides,polyimides, polyamidoimides, polysulfones, aromatic polyamides,polybenzooxazoles, and the like. Supports having a glass transitiontemperature of equal to or higher than 100° C. are preferably employed.The use of polyethylene naphthalate, aramid, or some other high-strengthsupport is particularly desirable. As needed, layered supports such asdisclosed in Japanese Unexamined Patent Publication (KOKAI) Heisei No.3-224127, which is expressly incorporated herein by reference in itsentirety, may be employed to vary the surface roughness of the magneticsurface and support surface. These supports may be subjected beforehandto corona discharge treatment, plasma treatment, adhesion enhancingtreatment, heat treatment, dust removal, and the like.

The center surface average surface roughness (Ra) of the nonmagneticsupport as measured with an optical interferotype surface roughnessmeter HD-2000 made by WYKO is preferably equal to or less than 8.0 nm,more preferably equal to or less than 4.0 nm, further preferably equalto or less than 2.0 nm. Not only does such a support desirably have alow center surface average surface roughness (Ra), but there are alsodesirably no large protrusions equal to or higher than 0.5 μm. Thesurface roughness shape may be freely controlled through the size andquantity of filler added to the support as needed. Examples of suchfillers are oxides and carbonates of elements such as Ca, Si, and Ti,and organic powders such as acrylic-based one. The support desirably hasa maximum height R_(max) equal to or less than 1 μm, a ten-point averageroughness R_(Z) equal to or less than 0.5 μm, a center surface peakheight R_(P) equal to or less than 0.5 μm, a center surface valley depthR_(V) equal to or less than 0.5 μm, a center-surface surface areapercentage Sr of 10 percent to 90 percent, and an average wavelengthλ_(a) of 5 to 300 μm. To achieve desired electromagnetic characteristicsand durability, the surface protrusion distribution of the support canbe freely controlled with fillers. It is possible to control within arange from 0 to 2,000 protrusions of 0.01 to 1 μm in size per 0.1 mm².

The F-5 value of the nonmagnetic support suitable for use in the presentinvention desirably ranges from 5 to 50 kg/mm², approximately 49 to 490MPa. The thermal shrinkage rate of the support after 30 min at 100° C.is preferably equal to or less than 3 percent, more preferably equal toor less than 1.5 percent. The thermal shrinkage rate after 30 min at 80°C. is preferably equal to or less than 1 percent, more preferably equalto or less than 0.5 percent. The breaking strength of the nonmagneticsupport preferably ranges from 5 to 100 kg/mm², approximately 49 to 980MPa. The modulus of elasticity preferably ranges from 100 to 2,000kg/mm², approximately 0.98 to 19.6 GPa. The thermal expansioncoefficient preferably ranges from 10⁴ to 10⁻⁸/° C., more preferablyfrom 10⁻⁵ to 10⁻⁶/° C. The moisture expansion coefficient is preferablyequal to or less than 10⁻⁴/RH percent, more preferably equal to or lessthan 10⁻⁵/RH percent. These thermal characteristics, dimensionalcharacteristics, and mechanical strength characteristics are desirablynearly equal, with a difference equal to less than 10 percent, in allin-plane directions in the support.

(Preparation of Coating Liquid)

The process for manufacturing coating liquids for magnetic andnonmagnetic layers can comprise at least a kneading step, a dispersingstep, and a mixing step to be carried out, if necessary, before and/orafter the kneading and dispersing steps. Each of the individual stepsmay be divided into two or more stages. All of the starting materialsemployed in the present invention, including the ferromagnetic powder,nonmagnetic powder, binders, carbon black, abrasives, antistatic agents,lubricants, solvents, and the like, may be added at the beginning of, orduring, any of the steps. Moreover, the individual starting materialsmay be divided up and added during two or more steps. For example,polyurethane may be divided up and added in the kneading step, thedispersion step, and the mixing step for viscosity adjustment afterdispersion. To achieve the object of the present invention,conventionally known manufacturing techniques may be utilized for someof the steps. A kneader having a strong kneading force, such as an openkneader, continuous kneader, pressure kneader, or extruder is preferablyemployed in the kneading step. When a kneader is employed, theferromagnetic powder or nonmagnetic powder and all or part of the binder(preferably equal to or higher than 30 weight percent of the entirequantity of binder) can be kneaded in a range of 15 to 500 parts per 100parts of the ferromagnetic powder. Details of the kneading process aredescribed in Japanese Unexamined Patent Publication (KOKAI) Heisei Nos.1-106338 and 1-79274, which are expressly incorporated herein byreference in their entirety. Further, glass beads may be employed todisperse the coating liquids for magnetic and nonmagnetic layers, with adispersing medium with a high specific gravity such as zirconia beads,titania beads, and steel beads being suitable for use. The particlediameter and fill ratio of these dispersing media can be optimized foruse. A known dispersing device may be employed.

In the method of manufacturing a magnetic recording medium, for example,a magnetic layer can be formed by coating a magnetic layer coatingliquid to a prescribed thickness on the surface of a nonmagnetic supportthat is being run. Multiple magnetic layer coating liquids can besuccessively or simultaneously coated in a multilayer coating, or anonmagnetic layer coating liquid and a magnetic layer coating liquid canbe successively or simultaneously coated in a multilayer coating.Coating machines suitable for use in coating the magnetic layer ornonmagnetic layer coating liquid are air doctor coaters, blade coaters,rod coaters, extrusion coaters, air knife coaters, squeeze coaters,immersion coaters, reverse roll coaters, transfer roll coaters, gravurecoaters, kiss coaters, cast coaters, spray coaters, spin coaters, andthe like. For example, “Recent Coating Techniques” (May 31, 1983),issued by the Sogo Gijutsu Center K.K. may be referred to in thisregard. The content of the above publication is expressly incorporatedherein by reference in its entirety.

For a magnetic tape, the coating layer that is formed by applying themagnetic layer coating liquid can be magnetic field orientationprocessed using cobalt magnets or solenoids on the ferromagnetic powdercontained in the coating layer. In the case of a disk, adequatelyisotropic orientation can sometimes be achieved with no orientationwithout using an orienting device. However, the diagonal arrangement ofcobalt magnets in alternating fashion or the use of a known randomorienting device such as a solenoid to apply an a.c. magnetic field isdesirable. In the case of a ferromagnetic metal powder, the term“isotropic orientation” generally means randomness in the two in-planedimensions, but can also be three-dimensional randomness when thevertical component is included. A known method such as magnets withopposite poles positioned opposite each other can also be employed toimpart isotropic magnetic characteristics in a circumferential directionby effecting vertical orientation. When conducting particularlyhigh-density recording, vertical orientation is desirable. Spin coatingcan also be employed to effect circumferential orientation.

The drying position of the coating is desirably controlled bycontrolling the temperature and flow rate of drying air, and coatingspeed. A coating speed of 20 m/min to 1,000 m/min and a dry airtemperature of equal to or higher than 60° C. are desirable. Suitablepredrying can be conducted prior to entry into the magnet zone.

The coated stock material obtained in this manner is normallytemporarily rolled on a pickup roll, and after a period, wound off thepickup roll and subjected to calendering.

In calendering, super calender rolls or the like can be employed.Calendering can enhance the smoothness of the surface, eliminate voidsproduced by removing the solvent during drying, and increase the fillrate of ferromagnetic powder in the magnetic layer, yielding a magneticrecording medium with good electromagnetic characteristics. Thecalendering step is desirably conducted by varying the calenderingconditions based on the smoothness of the surface of the coated stockmaterial.

The surface smoothness of the coated stock material can be controlled bymeans of the calender roll temperature, calender roll speed, andcalender roll tension. The calender roll pressure and calender rolltemperature are desirably controlled by taking into account thecharacteristics of the particulate medium. Lowering the calender rollpressure or calender roll temperature can decrease the surfacesmoothness of the final product. Conversely, raising the calender rollpressure or calender roll temperature can increase the surfacesmoothness of the final product.

Additionally, following the calendering step, the magnetic recordingmedium can be thermally processed to cause thermosetting to proceed.Such thermal processing can be suitably determined based on the blendingformula of the magnetic layer coating liquid. An example is 35 to 100°C., desirably 50 to 80° C. The thermal processing period is, forexample, 12 to 72 hours, desirably 24 to 48 hours.

Calender rolls made of epoxy, polyimide, polyamide, polyamideimide, andother heat-resistant plastic rolls can be employed. Processing can alsobe conducted with metal rolls.

Among the calendering conditions, the calender roll temperature, forexample, falls within a range of 60 to 100° C., desirably a range of 70to 100° C., and preferably a range of 80 to 100° C. The pressure, forexample, falls within a range of 100 to 500 kg/cm (approximately 98 to490 kN/m), preferably a range of 200 to 450 kg/cm (approximately 196 to441 kN/m), and preferably a range of 300 to 400 kg/cm (approximately 294to 392 kN/m). To increase the smoothness of the magnetic layer surface,the nonmagnetic layer surface can also be calendered. Calendering of thenonmagnetic layer is also desirably conducted under the aboveconditions.

The magnetic recording medium that is obtained can be cut to desiredsize with a cutter or the like for use. The cutter is not specificallylimited, but desirably comprises multiple sets of a rotating upper blade(male blade) and lower blade (female blade). The slitting speed,engaging depth, peripheral speed ratio of the upper blade (male blade)and lower blade (female blade) (upper blade peripheral speed/lower bladeperipheral speed), period of continuous use of slitting blade, and thelike can be suitably selected.

Physical Characteristics

Extremely good surface smoothness can be achieved in the magneticrecording medium of the present invention by incorporating the abovepolyurethane resin as a constituent component of the binder. The surfacesmoothness of the magnetic recording medium of the present inventiondesirably falls within a range of 0.1 to 4 nm, preferably 1 to 3 nm, asthe center surface average roughness of the magnetic layer surface. Theten-point average roughness R_(Z) on the surface of the magnetic layeris desirably equal to or less than 30 nm. The surface properties of themagnetic layer can be controlled by means of fillers added to thesupport, the surface shape of calender rolls, and the like. Curling ispreferably controlled to within ±3 mm.

The saturation magnetic flux density of the magnetic layer preferablyranges from 100 to 400 mT. The coercivity (Hc) of the magnetic layer ispreferably 143.2 to 318.3 kA/m (approximately 1,800 to 4,000 Oe), morepreferably 159.2 to 278.5 kA/m (approximately 2,000 to 3,500 Oe).Narrower coercivity distribution is preferable. The SFD and SFDr arepreferably equal to or lower than 0.6, more preferably equal to or lowerthan 0.3.

The coefficient of friction of the magnetic recording medium of thepresent invention relative to the head is, for example, equal to or lessthan 0.50 and preferably equal to or less than 0.3 at temperaturesranging from −10° C. to 40° C. and humidity ranging from 0 percent to 95percent, the surface resistivity on the magnetic surface preferablyranges from 10⁴ to 10⁸ ohm/sq, and the charge potential preferablyranges from −500 V to +500 V. The modulus of elasticity at 0.5 percentextension of the magnetic layer preferably ranges from 0.98 to 19.6 GPa(approximately 100 to 2,000 kg/mm²) in each in-plane direction. Thebreaking strength preferably ranges from 98 to 686 MPa (approximately 10to 70 kg/mm²). The modulus of elasticity of the magnetic recordingmedium preferably ranges from 0.98 to 14.7 GPa (approximately 100 to1500 kg/mm²) in each in-plane direction. The residual elongation ispreferably equal to or less than 0.5 percent, and the thermal shrinkagerate at all temperatures below 100° C. is preferably equal to or lessthan 1 percent, more preferably equal to or less than 0.5 percent, andmost preferably equal to or less than 0.1 percent.

The glass transition temperature (i.e., the temperature at which theloss elastic modulus of dynamic viscoelasticity peaks as measured at 110Hz) of the magnetic layer preferably ranges from 50 to 180° C., and thatof the nonmagnetic layer preferably ranges from 0 to 180° C. The losselastic modulus preferably falls within a range of 1×10⁷ to 8×10⁸ Pa(approximately 1×10⁸ to 8×10⁹ dyne/cm²) and the loss tangent ispreferably equal to or less than 0.2. Adhesion failure tends to occurwhen the loss tangent becomes excessively large. These thermalcharacteristics and mechanical characteristics are desirably nearlyidentical, varying by equal to or less than 10 percent, in each in-planedirection of the medium.

The residual solvent contained in the magnetic layer is preferably equalto or less than 100 mg/m² and more preferably equal to or less than 10mg/m². The void ratio in the coated layers, including both thenonmagnetic layer and the magnetic layer, is preferably equal to or lessthan 30 volume percent, more preferably equal to or less than 20 volumepercent. Although a low void ratio is preferable for attaining highoutput, there are some cases in which it is better to ensure a certainlevel based on the object. For example, in many cases, larger void ratiopermits preferred running durability in disk media in which repeat useis important.

When the magnetic recording medium of the present invention comprisesboth a magnetic layer and a nonmagnetic layer, physical properties ofthe nonmagnetic layer and magnetic layer may be varied based on theobjective. For example, the modulus of elasticity of the magnetic layermay be increased to improve running durability while simultaneouslyemploying a lower modulus of elasticity than that of the magnetic layerin the nonmagnetic layer to improve the head contact of the magneticrecording medium.

EXAMPLES

The present invention will be described in detail below based onExamples. However, the present invention is not limited to the examples.The “parts” and “percent” given in Examples are weight parts and weightpercent unless specifically stated otherwise.

The solid components given below were measured by the following methods.

A 1.0 g quantity of sample was dried under conditions of 180° C./30minutes. After drying, the weight was adopted as the solid component.

1. Examples and Comparative Examples of the Mixture and the SolutionComposition Example 1

One hundred parts of 2-aminoethanesulfonic acid and 26.8 parts oflithium hydroxide monohydrate were added to 250 parts of water and themixture was stirred for 30 minutes at 45° C. To this were added 156parts of 1,2-butylene oxide, and the mixture was stirred for 2 hours at45° C. After adding 400 parts of toluene and stirring for 10 minutes,the mixture was left standing and the lower layer was fractionated. Thelower layer obtained was solidified and dried, yielding a mixture ofsulfonate group-containing compound (S-1) and an acid form in which thelithium in (S-1) was hydrogen atoms. The mixture ratio (weight ratio) ofExample Compound (S-1) (base form) and the acid form calculated from thequantities used in preparation was base form:acid form=80:20.

Example 2

The 26.8 parts of lithium hydroxide monohydrate employed were replacedwith 25.6 parts of sodium hydroxide and the same operation was conductedas in Example 1 to obtain a mixture of Example Compound (S-19) and anacid form in which the sodium in (S-19) was hydrogen atoms. The mixtureratio (weight ratio) of Example Compound (S-19) (base form) and the acidform calculated from the quantities used in preparation was baseform:acid form=80:20.

Example 3

The 26.8 parts of lithium hydroxide monohydrate employed were replacedwith 37.8 parts of potassium hydroxide (95 percent purity) and the sameoperation was conducted as in Example 1 to obtain a mixture of ExampleCompound (S-20) and an acid form in which the sodium in (S-20) washydrogen atoms. The mixture ratio (weight ratio) of Example Compound(S-20) (base form) and the acid form calculated from the quantities usedin preparation was base form:acid form=80:20.

Comparative Example 1

The 26.8 parts of lithium hydroxide monohydrate were replaced with 33.5parts of lithium hydroxide and the same operation was conducted as inExample 1 to obtain Example Compound (S-1).

Comparative Example 2

The quantity of sodium hydroxide employed was changed to 32.0 parts andthe same operation was conducted as in Example 2 to obtain ExampleCompound (S-19).

Comparative Example 3

The quantity of potassium hydroxide (95 percent purity) employed waschanged to 47.2 parts and the same operation was conducted as in Example3 to obtain Example Compound (S-20).

Example 4

One hundred parts of 2-aminoethanesulfonic acid and 26.8 parts oflithium hydroxide monohydrate were added to 250 parts of water and themixture was stirred for 30 minutes at 45° C. To this were added 282parts of butyl glycidyl ether, and the mixture was stirred for 2 hoursat 45° C. After adding 400 parts of toluene and stirring for 10 minutes,the mixture was left standing and the lower layer was fractionated. Thelower layer obtained was solidified and dried, yielding a mixture of anExample Compound (S-2) and an acid form in which the lithium in (S-2)was hydrogen atoms. The mixture ratio (weight ratio) of Example Compound(S-2) (base form) and the acid form calculated from the quantities usedin preparation was base form:acid form=80:20.

Example 5

The 26.8 parts of lithium hydroxide monohydrate employed were replacedwith 25.6 parts of sodium hydroxide and the same operation was conductedas in Example 4 to obtain a mixture of Example Compound (S-21) and anacid form in which the sodium in (S-21) was hydrogen atoms. The mixtureratio (weight ratio) of Example Compound (S-21) (base form) and the acidform calculated from the quantities used in preparation was baseform:acid form=80:20.

Example 6

The 26.8 parts of lithium hydroxide monohydrate employed were replacedwith 37.8 parts of potassium hydroxide (95 percent purity) and the sameoperation was conducted as in Example 4 to obtain a mixture of ExampleCompound (S-22) and an acid form in which the potassium in (S-22) washydrogen atoms. The mixture ratio (weight ratio) of Example Compound(S-22) (base form) and the acid form calculated from the quantities usedin preparation was base form:acid form=80:20.

Comparative Example 4

The 26.8 parts of lithium hydroxide monohydrate were replaced with 33.5parts of lithium hydroxide and the same operation was conducted as inExample 4 to obtain Example Compound (S-2).

Comparative Example 5

The quantity of sodium hydroxide employed was changed to 32.0 parts andthe same operation was conducted as in Example 5 to obtain ExampleCompound (S-21).

Comparative Example 6

The quantity of potassium hydroxide (95 percent purity) employed waschanged to 37.8 parts and the same operation was conducted as in Example6 to obtain Example Compound (S-22).

Example 7

To 1.0 part of Example Compound (S-1) obtained in Comparative Example 1were added 0.21 part of acetic acid and 0.79 part of toluene to preparea solution with 50 percent solid component.

Example 8

To 1.0 part of Example Compound (S-19) obtained in Comparative Example 2were added 0.21 part of acetic acid and 0.79 part of toluene to preparea solution with 50 percent solid component.

Example 9

To 1.0 part of Example Compound (S-20) obtained in Comparative Example 3were added 0.20 part of acetic acid and 0.80 part of toluene to preparea solution with 50 percent solid component.

Example 10

To 1.0 part of Example Compound (S-2) obtained in Comparative Example 4were added 0.15 part of acetic acid and 0.85 part of toluene to preparea solution with 50 percent solid component.

Example 11

To 1.0 part of (S-21) obtained by the method of the Example Compoundobtained in Comparative Example 5 were added 0.15 part of acetic acidand 0.85 part of toluene to prepare a solution with 50 percent solidcomponent.

Example 12

To 1.0 part of Example Compound (S-22) obtained in Comparative Example 6were added 0.14 part of acetic acid and 0.86 part of toluene to preparea solution with 50 percent solid component.

Example 13

With the exception that the 0.79 part of toluene was replaced with 0.79part of cyclohexanone, a solution with 50 percent solid component wasprepared by the same method as in Example 7.

Example 14

With the exception that the 0.79 part of toluene was replaced with 0.79part of cyclohexanone, a solution with 50 percent solid component wasprepared by the same method as in Example 8.

Example 15

With the exception that the 0.80 part of toluene was replaced with 0.80part of cyclohexanone, a solution with 50 percent solid component wasprepared by the same method as in Example 9.

Example 16

With the exception that the 0.85 part of toluene was replaced with 0.85part of cyclohexanone, a solution with 50 percent solid component wasprepared by the same method as in Example 10.

Example 17

With the exception that the 0.85 part of toluene was replaced with 0.85part of cyclohexanone, a solution with 50 percent solid component wasprepared by the same method as in Example 11.

Example 18

With the exception that the 0.86 part of toluene was replaced with 0.86part of cyclohexanone, a solution with 50 percent solid component wasprepared by the same method as in Example 12.

Example 19

With the exceptions that the 0.21 part of acetic acid and 0.79 part oftoluene were replaced with 0.52 part of octanoic acid and 0.48 part oftoluene, a solution with 50 percent solid component was prepared by thesame method as in Example 7.

Example 20

With the exceptions that the 0.21 part of acetic acid and 0.79 part oftoluene were replaced with 0.49 part of octanoic acid and 0.61 part oftoluene, a solution with 50 percent solid component was prepared by thesame method as in Example 8.

Example 21

With the exceptions that the 0.21 part of acetic acid and 0.79 part oftoluene were replaced with 0.47 part of octanoic acid and 0.53 part oftoluene, a solution with 50 percent solid component was prepared by thesame method as in Example 9.

Example 22

With the exceptions that the 0.21 part of acetic acid and 0.79 part oftoluene were replaced with 0.37 part of octanoic acid and 0.63 part oftoluene, a solution with 50 percent solid component was prepared by thesame method as in Example 10.

Example 23

With the exceptions that the 0.21 part of acetic acid and 0.79 part oftoluene were replaced with 0.35 part of octanoic acid and 0.65 part oftoluene, a solution with 50 percent solid component was prepared by thesame method as in Example 11.

Example 24

With the exceptions that the 0.21 part of acetic acid and 0.79 part oftoluene were replaced with 0.34 part of octanoic acid and 0.66 part oftoluene, a solution with 50 percent solid component was prepared by thesame method as in Example 12.

Identification of the product NMR data and data assignment for themixture obtained in Example 1 are given below. A 400 MHz NMR (AVANCE11-400 made by BRUKER) was employed in the ¹H NMR measurement conductedin the present Example.

¹H NMR (D₂0=4.75 ppm) δ (ppm)=3.68 (2H, m), 3.10 (2H, m), 2.59 (2H, m),2.40 (4H, m), 1.45 (4H, m), 0.89 (6H, t).

¹H NMR data and data assignment for Example Compound (S-1) obtained inComparative Example 1 are given below.

¹H NMR (D₂0=4.75 ppm) δ (ppm)=3.68 (2H, m), 3.10 (2H, m), 2.59 (2H, m),2.40 (4H, m), 1.45 (4H, m), 0.89 (6H, t).

¹H NMR data for the mixture obtained in Example 7 are given below.

¹H NMR (D₂O=4.75 ppm) δ (ppm)=3.68 (2H, m), 3.10 (2H, m), 2.59 (2H, m),2.40 (4H, m), 1.91 (1.2H,$), 1.45 (4H, m), 0.89 (6H, t).

In Example 7, no proton shift was observed in ¹H NMR following theaddition of acetic acid. ¹H NMR data and data assignment for acetic acidare given below.

Acetic acid: 1.91 (1.2H, s)

NMR data and data assignment for the mixture obtained in Example 4 aregiven below.

¹H NMR (D₂O=4.75 ppm) δ (ppm)=3.84 (2H, m), 3.55-3.30 (8H, m), 3.38 (2H,m), 2.95 (4H, m), 2.51 (2H, m), 1.49 (4H, m), 1.27 (4H, m), 0.83 (6H,t).

Examples 25 to 30

One part of each of the mixtures obtained in Examples 1 to 6 wasseparately dissolved in one part of toluene to obtain solutions with 50percent solid component.

Examples 31 to 36

One part of each of the mixtures obtained in Examples 1 to 6 wasseparately dissolved in one part of cyclohexanone to obtain solutionswith 50 percent solid component.

Comparative Examples 7 to 12

One part of each of Example Compound obtained in Comparative Examples 1to 6 was separately dissolved in one part of toluene to obtain solutionswith 50 percent solid component.

Evaluation of Solution Stability

The pH of each of the solutions obtained in Examples 7 to 36 wasmeasured within one day of preparation and two months after preparation.The results are given in Table 1 below. Visual observation of thesolutions obtained revealed them to be transparent.

TABLE 1 Example pH Compound Change (sulfonate With- in group- in AfterpH containing Protonic Organic one two over Solution compound) acidsolvent day months time Ex.25 (S-1)  Acid Toluene 8 7.9 0.1 form Ex.26(S-19) Acid Toluene 8 8 0 form Ex.27 (S-20) Acid Toluene 8 8 0 formEx.28 (S-2)  Acid Toluene 8 7.9 0.1 form Ex.29 (S-21) Acid Toluene 7.87.7 0.1 form Ex.30 (S-22) Acid Toluene 8 8 0 form Ex.31 (S-1)  AcidCyclo- 8 7.9 0.1 form hexanone Ex.32 (S-19) Acid Cyclo- 8 8 0 formhexanone Ex.33 (S-20) Acid Cyclo- 8 8 0 form hexanone Ex.34 (S-2)  AcidCyclo- 8 7.9 0.1 form hexanone Ex.35 (S-21) Acid Cyclo- 7.8 7.7 0.1 formhexanone Ex.36 (S-22) Acid Cyclo- 8 8 0 form hexanone  Ex.7 (S-1) Acetic Toluene 8 8 0 acid  Ex .8 (S-19) Acetic Toluene 7.2 7.2 0 acid Ex .9 (S-20) Acetic Toluene 8 8 0 acid Ex.10 (S-2)  Acetic Toluene 7.27.2 0 acid Ex.11 (S-21) Acetic Toluene 8 8 0 acid Ex.12 (S-22) AceticToluene 7.2 7.2 0 acid Ex.13 (S-1)  Acetic Cyclo- 8.3 8 0.3 acidhexanone Ex.14 (S-19) Acetic Cyclo- 7.6 7.2 0.4 acid hexanone Ex.15(S-20) Acetic Cyclo- 8.3 8 0.3 acid hexanone Ex.16 (S-2)  Acetic Cyclo-7.6 7.2 0.4 acid hexanone Ex.17 (S-21) Acetic Cyclo- 8.3 8 0.3 acidhexanone Ex.18 (S-22) Acetic Cyclo- 7.6 7.2 0.4 acid hexanone Ex.19(S-1)  Octanoic Toluene 8.3 8 0.3 acid Ex.20 (S-19) Octanoic Toluene 7.67.2 0.4 acid Ex.21 (S-20) Octanoic Toluene 8.3 8 0.3 acid Ex.22 (S-2) Octanoic Toluene 7.6 7.2 0.4 acid Ex.23 (S-21) Octanoic Toluene 8.3 80.3 acid Ex.24 (S-22) Octanoic Toluene 7.3 7.2 0.4 acid Comp. (S-1) None Toluene 11.2 9.2 2 Ex.1 Comp. (S-19) None Toluene 10.9 9.6 1.3 Ex.2Comp. (S-20) None Toluene 11 9.3 1.7 Ex.3 Comp. (S-2)  None Toluene 10.99.2 1.7 Ex.4 Comp. (S-21) None Toluene 10.9 9.2 1.7 Ex.5 Comp. (S-22)None Toluene 10.9 9.2 1.7 Ex.6

Based on the results in Table 1, the solutions obtained in Examples wereall determined to have good storage stability with little change in pHover time.

2. Polyurethane Resin Examples Example 37

To 150 parts of cyclohexanone were added 2.2 parts of the mixtureprepared in Example 3, 34.4 parts of polyether (Adeka polyether BPX-1000made by Adeka Corp.), 27.2 parts oftricyclo[5,2,1,0(2,6)]decanedimethanol (made by Tokyo Chemical IndustryCo., Ltd.), and 0.1 part of dibutyltin dilaurate, and the mixture wasstirred for 30 minutes at room temperature and fully dissolved. Themoisture within the flask was measured with a Karl Fischer moistureanalyzer and an equimolar quantity of diphenylmethane diisocyanate(Millionate MT, made by Nippon Polyurethane Industry Co., Ltd.) wasadded for the water content. The internal temperature was set to 80° C.and 36.3 parts of diphenylmethane diisocyanate (Millionate MT, made byNippon Polyurethane Industry Co., Ltd.) were added. The mixture wasstirred for 4 hours at an internal temperature of 80 to 90° C. and thencooled to room temperature.

The weight average molecular weight and the weight average molecularweight/number average molecular weight (Mw/Mn) of the polyurethaneobtained were obtained by standard polystyrene conversion using DMFsolvent containing 0.3 weight percent of lithium bromide. The weightaverage molecular weight was 70,000 and the Mw/Mn was 1.90. The sulfonicacid (salt) group content of the polyurethane obtained as measured bythe following method was 6×10⁻⁴ eq/g.

A sulfur preparation in the form of 1.0 weight part of copper sulfatepentahydrate (made by Wako Pure Chemical Industries, Ltd.) was dissolvedin 49.0 weight parts of pure water. A 200 microliter quantity of thesolution obtained was added dropwise to a filter paper with circle 30 mmin diameter, made by Shimadzu Corp., and dried for three hours atordinary temperature under a vacuum. The luminous intensity of thesulfur was measured with a fluorescence X-ray analyzer, the LAB CENTERXRF-1700, made by Shimadzu Corp. Solutions in which the copper sulfatepentahydrate and water employed were changed to 0.1 weight part:49.9weight parts and 0.5 weight part:49.5 weight parts were prepared, theluminous intensity of the sulfur was measured, and a calibration curvewas plotted.

A 1.0 weight part quantity of polyurethane was dissolved in 49.0 weightparts of cyclohexanone. By the same method, the polyurethane solutionwas added dropwise to a filter paper with circle made by Shimadzu Corp.,dried, and measured to determine the luminous intensity of the sulfur.The sulfur luminous intensity of the polyurethane solution was comparedto that of the copper sulfate pentahydrate calibration curve, and thequantity of sulfonic acid (salt) groups contained in the polyurethanewas determined.

Evaluation of Dispersibility

A 4.1 part quantity of the nonmagnetic powder indicated below and onepart of the polyurethane synthesized in Example 37 were suspended in asolution comprised of 10.8 parts of cyclohexanone and 16.2 parts of2-butanone. To the suspension were added 90 parts of zirconia beads(made by Nikkato Corp.) and the mixture was dispersed for six hours. Thesolution obtained was coated on a polyethylene naphthalate (PEN) filmmade by Teijin (Ltd.) and dried to prepare a sheet. Measurement of theglossiness of the sheet resulted in a value of 191. The higher theglossiness, the better the powder dispersion indicated. The glossinesswas measured with a GK-45D made by Suga Test Instruments Co., Ltd.

Nonmagnetic powder: α-iron oxide (surface treatment layers: Al₂O₃, SiO₂)

Average major axis length: 0.15 μm

Average acicular ratio: 7

Specific surface area by the BET method: 52 m²/g

pH 8

Example 38

To 54.1 parts of cyclohexanone were added 3.0 parts of the mixtureprepared in Example 5, 33.3 parts of polyether (Adeka polyether BPX-1000made by Adeka Corp.), 27.5 parts oftricyclo[5,2,1,0(2,6)]decanedimethanol (made by Tokyo Chemical IndustryCo., Ltd.), and 0.1 part of dibutyltin dilaurate, and the mixture wasstirred for 30 minutes at room temperature and fully dissolved. Themoisture within the flask was measured with a Karl Fischer moistureanalyzer and an equimolar quantity of diphenylmethane diisocyanate(Millionate MT, made by Nippon Polyurethane Industry Co., Ltd.) wasadded for the water content. The internal temperature was set to 80° C.and 36.3 parts of diphenylmethane diisocyanate (Millionate MT, made byNippon Polyurethane Industry Co., Ltd.) were added. The mixture wasstirred for 4 hours at an internal temperature of 80 to 90° C. and thencooled to room temperature.

The weight average molecular weight and the weight average molecularweight/number average molecular weight (Mw/Mn) of the polyurethaneobtained were measured by the same method as in Example 37, revealing aweight average molecular weight of 70,000 and an Mw/Mn of 1.90. Thesulfonic acid (salt) group content of the polyurethane obtained asmeasured by the above-described method was 6×10⁻⁴ eq/g.

A sheet was prepared and the glossiness was measured by the same methodsas in Example 37 using the polyurethane obtained, revealing a glossinessof 189.

Example 39

To 150 parts of cyclohexanone were added 2.2 parts of the mixtureprepared in Example 3, 38.3 parts of polyether (Adeka polyether BPX-1000made by Adeka Corp.), 18.4 parts oftricyclo[5,2,1,0(2,6)]decanedimethanol (made by Tokyo Chemical IndustryCo., Ltd.), 4.8 parts glycerol monomethacrylate (Blemmer GLM, made byNOF Corporation), and 0.1 part of dibutyltin dilaurate, and the mixturewas stirred for 30 minutes at room temperature and fully dissolved. Themoisture within the flask was measured with a Karl Fischer moistureanalyzer and an equimolar quantity of diphenylmethane diisocyanate(Millionate MT, made by Nippon Polyurethane Industry Co., Ltd.) wasadded for the water content. The internal temperature was set to 80° C.and 36.3 parts of diphenylmethane diisocyanate (Millionate MT, made byNippon Polyurethane Industry Co., Ltd.) were added. The mixture wasstirred for 4 hours at an internal temperature of 80 to 90° C. and thencooled to room temperature.

The weight average molecular weight and the weight average molecularweight/number average molecular weight (Mw/Mn) of the polyurethaneobtained were measured by the same method as in Example 37, revealing aweight average molecular weight of 70,000 and an Mw/Mn of 1.90. Thesulfonic acid (salt) group content of the polyurethane obtained asmeasured by the above-described method was 6×10⁻⁴ eq/g.

A sheet was prepared and the glossiness was measured by the same methodsas in Example 37 using the polyurethane obtained, revealing a glossinessof 191.

Example 40

To 54.1 parts of cyclohexanone were added 3.0 parts of the mixtureprepared in Example 5, 37.3 parts of polyether (Adeka polyether BPX-1000made by Adeka Corp.), 18.7 parts oftricyclo[5,2,1,0(2,6)]decanedimethanol (made by Tokyo Chemical IndustryCo., Ltd.), 4.8 parts glycerol monomethacrylate (Blemmer GLM, made byNOF Corporation), and 0.1 part of dibutyltin dilaurate, and the mixturewas stirred for 30 minutes at room temperature and fully dissolved. Themoisture within the flask was measured with a Karl Fischer moistureanalyzer and an equimolar quantity of diphenylmethane diisocyanate(Millionate MT, made by Nippon Polyurethane Industry Co., Ltd.) wasadded for the water content. The internal temperature was set to 80° C.and 36.3 parts of diphenylmethane diisocyanate (Millionate MT, made byNippon Polyurethane Industry Co., Ltd.) were added. The mixture wasstirred for 4 hours at an internal temperature of 80 to 90° C. and thencooled to room temperature.

The weight average molecular weight and the weight average molecularweight/number average molecular weight (Mw/Mn) of the polyurethaneobtained were measured by the same method as in Example 37, revealing aweight average molecular weight of 70,000 and an Mw/Mn of 1.90. Thesulfonic acid (salt) group content of the polyurethane obtained asmeasured by the above-described method was 6×10⁻⁴ eq/g.

A sheet was prepared and the glossiness was measured by the same methodsas in Example 37 using the polyurethane obtained, revealing a glossinessof 189.

Example 41

To 54.1 parts of cyclohexanone were added 3.0 parts of the mixtureprepared in Example 6, 37.3 parts of polyether (Adeka polyether BPX-1000made by Adeka Corp.), 18.7 parts oftricyclo[5,2,1,0(2,6)]decanedimethanol (made by Tokyo Chemical IndustryCo., Ltd.), 4.8 parts glycerol monomethacrylate (Blemmer GLM, made byNOF Corporation), and 0.1 part of dibutyltin dilaurate, and the mixturewas stirred for 30 minutes at room temperature and fully dissolved. Themoisture within the flask was measured with a Karl Fischer moistureanalyzer and an equimolar quantity of diphenylmethane diisocyanate(Millionate MT, made by Nippon Polyurethane Industry Co., Ltd.) wasadded for the water content. The internal temperature was set to 80° C.and 36.3 parts of diphenylmethane diisocyanate (Millionate MT, made byNippon Polyurethane Industry Co., Ltd.) were added. The mixture wasstirred for 4 hours at an internal temperature of 80 to 90° C. and thencooled to room temperature.

The weight average molecular weight and the weight average molecularweight/number average molecular weight (Mw/Mn) of the polyurethaneobtained were measured by the same method as in Example 37, revealing aweight average molecular weight of 70,000 and an Mw/Mn of 1.90. Thesulfonic acid (salt) group content of the polyurethane obtained asmeasured by the above-described method was 6×10⁻⁴ eq/g.

A sheet was prepared and the glossiness was measured by the same methodsas in Example 37 using the polyurethane obtained, revealing a glossinessof 193.

Comparative Example 7

To 54.1 parts of N-methylpyrrolidone were added 5.7 parts of thesulfonate group-containing compound (weight average molecularweight=4,500) comprising polyester of the structure indicated below,35.7 parts of polyether (Adeka polyether BPX-1000 made by Adeka Corp.),22.4 parts of tricyclo[5,2,1,0(2,6)]decanedimethanol (made by TokyoChemical Industry Co., Ltd.), and 0.1 part of dibutyltin dilaurate, andthe mixture was stirred for 30 minutes at room temperature and fullydissolved. The moisture within the flask was measured with a KarlFischer moisture analyzer and an equimolar quantity of diphenylmethanediisocyanate (Millionate MT, made by Nippon Polyurethane Industry Co.,Ltd.) was added for the water content. The internal temperature was setto 80° C. and 71.9 parts of N-methylpyrrolidone solution containing 50weight percent of diphenylmethane diisocyanate (Millionate MT, made byNippon Polyurethane Industry Co., Ltd.) were added at a rate yielding aninternal temperature of 80 to 90° C. The mixture was stirred for 4 hoursat an internal temperature of 80 to 90° C. and then cooled to roomtemperature.

The weight average molecular weight and the weight average molecularweight/number average molecular weight (Mw/Mn) of the polyurethaneobtained were measured by the same method as in Example 37, revealing aweight average molecular weight of 70,000 and an Mw/Mn of 1.90.

A sheet was prepared and the glossiness was measured by the same methodsas in Example 37 using the polyurethane obtained, revealing a glossinessof 145.

Example 42

To 54.1 parts of N-methylpyrrolidone were added 1.7 parts of the mixtureprepared in Example 1, 40.7 parts of polyether (Adeka polyether BPX-1000made by Adeka Corp.), and 21.4 parts oftricyclo[5,2,1,0(2,6)]decanedimethanol (made by Tokyo Chemical IndustryCo., Ltd.) and the mixture was stirred for 30 minutes at roomtemperature and fully dissolved. The moisture within the flask wasmeasured with a Karl Fischer moisture analyzer and an equimolar quantityof diphenylmethane diisocyanate (Millionate MT, made by NipponPolyurethane Industry Co., Ltd.) was added for the water content. Theinternal temperature was set to 80° C. and 71.9 parts ofN-methylpyrrolidone solution containing 50 weight percent ofdiphenylmethane diisocyanate (Millionate MT, made by Nippon PolyurethaneIndustry Co., Ltd.) were added at a rate yielding an internaltemperature of 80 to 90° C. The mixture was stirred for 4 hours at aninternal temperature of 80 to 90° C. and then cooled to roomtemperature.

The weight average molecular weight and the weight average molecularweight/number average molecular weight (Mw/Mn) of the polyurethaneobtained were measured by the same method as in Example 37, revealing aweight average molecular weight of 70,000 and an Mw/Mn of 1.90. Thesulfonic acid (salt) group content of the polyurethane obtained asmeasured by the above-described method was 6×10⁻⁴ eq/g.

A 7.3 part quantity of the barium ferrite powder indicated below and 1part of the polyurethane synthesized above were suspended in a solutioncomprised of 11.9 parts of cyclohexanone and 17.7 parts of 2-butanone.To the suspension were added 90 parts of zirconia beads (made by NikkatoCorp.) and the mixture was dispersed for 6 hours. Measurement of theratio of the abundance of the dispersion solution polyurethane on thesurface of the barium ferrite powder/in the solution by the method setforth below revealed it to be 4.0/1. The sulfur content in the solutionas measured with fluorescence X-rays was below the threshold ofdetection. Since no sulfur derived from sulfonic acid (salt) groupscould be detected in the solution, the polyurethane synthesized as setforth above was determined to be nearly absent from the solution and tohave adsorbed nearly completely to the powder. Subsequently, the liquidobtained was coated and dried to prepare a sheet. The glossiness of thesheet was measured by the same method as that set forth above, revealinga glossiness of 171.

Ferromagnetic hexagonal barium ferrite powder

Composition excluding oxygen (mole ratio): Ba/Fe/Co/Zn=1/9/0.2/1

Hc: 176 kA/m (2,200 Oe)

Average particle diameter: 25 nm

Average plate ratio: 3

BET specific surface area: 65 m²/g

σs: 49 A·m²/kg (49 emu/g)

pH: 7

—Method of Measuring Abundance Ratio of Polyurethane—

The barium ferrite powder was centrifugally separated from thedispersion solution using a small separation-use ultracentrifuge CS150GXL made by Hitachi under conditions of 100,000 rpm for 80 minutes. A3 mL quantity of the supernatant was measured out and weighed. It wasthen dried under conditions of 40° C. for 18 hours, and then furtherdried under vacuum at 140° C. for 3 hours. The weight of the driedproduct was adopted as the non-adsorbed solid component of thepolyurethane. The abundance ratio of the polyurethane on the surface ofthe barium ferrite powder/in the solution was calculated from thepolyurethane observed in the supernatant and the polyurethane used inthe dispersion.

Comparative Example 8

To 54.1 parts of N-methylpyrrolidone were added 31.2 parts of thesulfonic acid compound (weight average molecular weight=4,500)comprising the polyester used to synthesize the polyurethane ofComparative Example 7, 35.7 parts of polyether (Adeka polyether BPX-1000made by Adeka Corp.), 21.9 parts oftricyclo[5,2,1,0(2,6)]decanedimethanol (made by Tokyo Chemical IndustryCo., Ltd.), and 0.1 part of dibutyltin dilaurate and the mixture wasstirred for 30 minutes at room temperature and fully dissolved. Themoisture within the flask was measured with a Karl Fischer moistureanalyzer and an equimolar quantity of diphenylmethane diisocyanate(Millionate MT, made by Nippon Polyurethane Industry Co., Ltd.) wasadded for the water content. The internal temperature was set to 80° C.and 71.9 parts of N-methylpyrrolidone solution containing 50 weightpercent of diphenylmethane diisocyanate (Millionate MT, made by NipponPolyurethane Industry Co., Ltd.) were added at a rate yielding aninternal temperature of 80 to 90° C. The mixture was stirred for 4 hoursat an internal temperature of 80 to 90° C. and then cooled to roomtemperature.

The weight average molecular weight and the weight average molecularweight/number average molecular weight (Mw/Mn) of the polyurethaneobtained were measured by the same method as in Example 37, revealing aweight average molecular weight of 70,000 and an Mw/Mn of 1.90.

A dispersion was prepared and the abundance ratio on the surface ofbarium ferrite powder/in the solution was measured by the same methodsas in Example 42 using the polyurethane obtained, yielding a ratio of2.6/1.

A sheet was prepared and the glossiness was measured by the same methodsas in Example 42 using the polyurethane obtained, revealing a glossinessof 145.

The mixture of the present invention is useful as a starting material invarious organic compound reactions, such as in the synthesis ofpolyurethane resins.

Although the present invention has been described in considerable detailwith regard to certain versions thereof, other versions are possible,and alterations, permutations and equivalents of the version shown willbecome apparent to those skilled in the art upon a reading of thespecification and study of the drawings. Also, the various features ofthe versions herein can be combined in various ways to provideadditional versions of the present invention. Furthermore, certainterminology has been used for the purposes of descriptive clarity, andnot to limit the present invention. Therefore, any appended claimsshould not be limited to the description of the preferred versionscontained herein and should include all such alterations, permutations,and equivalents as fall within the true spirit and scope of the presentinvention.

Having now fully described this invention, it will be understood tothose of ordinary skill in the art that the methods of the presentinvention can be carried out with a wide and equivalent range ofconditions, formulations, and other parameters without departing fromthe scope of the invention or any embodiments thereof.

All patents and publications cited herein are hereby fully incorporatedby reference in their entirety. The citation of any publication is forits disclosure prior to the filing date and should not be construed asan admission that such publication is prior art or that the presentinvention is not entitled to antedate such publication by virtue ofprior invention.

What is claimed is:
 1. A polyurethane resin, obtained from startingmaterials in the form of an isocyanate compound and a mixture or asolution composition comprised of an organic solvent in which themixture is dissolved, wherein the mixture is a mixture of a sulfonategroup-containing compound denoted by general formula (1) with a protonicacid:

wherein, in general formula (1), X denotes a divalent linking group;each of R¹ and R² independently denotes an alkyl group comprising atleast one hydroxyl group and equal to or more than three carbon atoms oran aralkyl group comprising at least one hydroxyl group and equal to ormore than eight carbon atoms; and M denotes a cation.
 2. Thepolyurethane resin according to claim 1, which comprises a sulfonic acid(salt) group in a quantity of 1×10⁻⁵ eq/g to 2×10⁻³ eq/g.
 3. Thepolyurethane resin according to claim 1, wherein the starting materialsfurther comprises a diol comprising a (meth)acryloyloxy group.
 4. Amethod of manufacturing a polyurethane resin, comprising: subjecting amixture or a solution composition comprised of an organic solvent inwhich the mixture is dissolved to an urethane-forming reaction with anisocyanate compound, wherein the mixture is a mixture of a sulfonategroup-containing compound denoted by general formula (1) with a protonicacid:

wherein, in general formula (1), X denotes a divalent linking group;each of R¹ and R² independently denotes an alkyl group comprising atleast one hydroxyl group and equal to or more than three carbon atoms oran aralkyl group comprising at least one hydroxyl group and equal to ormore than eight carbon atoms; and M denotes a cation.
 5. The method ofmanufacturing according to claim 4 wherein the urethane-forming reactionis conducted in the presence of a catalyst.
 6. The method ofmanufacturing according to claim 5 wherein the mixture or the solutioncomposition is subjected to the urethane-forming reaction after addingthe catalyst thereto.